Actinically-crosslinkable polysiloxane-polyglycerol block copolymers and methods of making and use thereof

ABSTRACT

Described herein are compositions comprising an actinically-crosslinkable polysiloxane-polyglycerol block copolymers, methods of making and use thereof, and devices comprising the compositions described herein. Disclosed herein are compositions comprising an actinically-crosslinkable polysiloxane-polyglycerol block copolymer derived from: a polysiloxane prepolymer comprising a polyglycerol side chain, the polyglycerol side chain comprising an ethylenically unsaturated group covalently linked thereto, wherein the ethylenically unsaturated group is actinically curable.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. ProvisionalApplication No. 62/966,233 filed Jan. 27, 2020, which is herebyincorporated herein by reference in its entirety.

BACKGROUND

Hydrogels have the ability to be shaped, as well as absorb and retainlarge amounts of water, which mimics natural tissues. Due to thesedistinctive characteristics, hydrogels have been recognized as importantbiomaterials in the fields of tissue engineering, regenerative medicine,medical device construction, coatings for medical devices, microfluidicdevices, extracellular matrices for 3D cell cultures, and drug deliveryapplications. However, hydrogel biomaterials have relatively poormechanical properties, which is a limiting factor associated withhydrogel biomaterials. Regulating the transport properties,hydrophilicity, and biomechanical properties of hydrogels is vital toproduct performance.

There remains a need in the art for cost effective and simplifiedmethods for producing medical devices such as silicone hydrogel contactlenses having lubricious and wear resistance surfaces. In addition, thedevices also need the combined characteristics of biocompatibility, lowtoxicity and low coefficient of friction in contact with body fluids,such as tears and blood.

Soft (hydrophilic) silicone hydrogel contact lenses provide improvedoxygen permeability as compared to soft non-silicone hydrogel contactlenses such as cross-linked poly(2-Hydroxyethyl methacrylate)(Polymacon). Initial efforts to make silicone hydrogel contact lenseswere plagued by substandard wettability, poor clarity, low water contentand high modulus. In addition, early silicone hydrogel contact lenseswere made from expensive custom-made raw materials. In order for firstgeneration silicone hydrogel contact lenses to achieve acceptablehydrophilicity, surface treatment methods (such as plasma surfacetreatments) were utilized to improve wettability of these materials(U.S. Pat. Nos. 6,213,604, 6,348,507, 6,200,626, 5,760,100, 5,849,811).

For example, commercial lenses such as Focus NIGHT & DAY™, AirOptix(Alcon), and PureVision™ (Bausch & Lomb) employ plasma surfacetreatments. Plasma surface treatments create a plasma coating at thetreated surface. Advantages of a plasma coating include durability,relatively high hydrophilicity (or good wettability), and, in the caseof plasma that produces non-ionic surfaces (Methane Plasma), lowsusceptibility to lipid and protein deposition and adsorption. However,plasma treatment of silicone hydrogel contact lenses may not be costeffective, especially in the case of single use contact lenses. One ofthe main reasons for this is high capital costs associated with highvolume production lines equipped with plasma equipment. In addition tohigh capital investment, contact lenses can require extraction anddrying prior to plasma treatment, thereby increasing complexity and costto the manufacturing process.

Another method for modifying the hydrophilicity of a relativelyhydrophobic contact lens material is a layer-by-layer (LBL) poly ionicmaterial deposition technique (U.S. Pat. Nos. 6,451,871, 6,717,929,6,793,973, 6,884,457, 6,896,926, 6,926,965, 6,940,580). Although LBL canprovide a cost-effective process for rendering a silicone hydrogelmaterial wettable, the dip coating baths employed in such processes areprone to cross contamination. Furthermore, LBL coatings are less durablethan chemically bonded coatings.

In U.S. Pat. No. 6,367,929 B1, Johnson & Johnson Vision Care, Inc.,describe producing wettable silicone hydrogel lenses by incorporatinginternal wetting agents into lens formulations. This patent states thata wettable silicone hydrogel is made by including a high molecularweight hydrophilic polymer into the silicone hydrogel monomer mix. Thepatent further states that the hydrophilic polymer is entrapped in thehydrogel matrix (little or no covalent bonding between internal wettingagent and the contact lens matrix). The use of internal wetting agentsin lens formulations allows for a simpler manufacturing process comparedto plasma treatment. However, there are some disadvantages to thisapproach. First, not all of the added wetting agent (PVP) is retained inthe contact lens. Secondly, silicone hydrogel contact lenses typicallyrequire extraction with organic solvent. Since the internally wettingagent is not chemically bonded to the lens matrix, it can be removed orpartially removed during extraction operations. Therefore, extraction oflenses containing non-chemically bound internal wetting agent (e.g.,PVP) requires careful control of extraction operations to ensure thefinal product contains the desired loading of the internal wettingagent. Third, the internal wetting agent used was PVP, which is watersoluble and therefore may continue to leach from the lens during use bycustomers. If too much PVP is lost due to leaching, contact lenslubricity may be compromised and contact lens dimensions may changethereby making it difficult to maintain product specifications andperformance. Contact lens formulations described in U.S. Pat. No.6,367,929 B1 contain two immiscible polymers (mono-methacrylatedpolydimethylsiloxane, and PVP). In order to achieve a homogeneoussolution of the two immiscible polymers, the use of solvent(s) and/orcompatibilizing agent(s) is necessary. Use of special compatibilizingagents, which may need to be custom manufactured, increases productcost. Combining two dissimilar polymers in a chemical mixture imposesconsiderable compositional limitations in achieving a homogenous clearsolution. Furthermore, homogeneous clear contact lens formulationscontaining two or more dissimilar polymers or copolymers are susceptibleto phase separation induced by changes in temperature, pressure, pH,ionic strength, and solvent quality. Phase separated formulations areinadequate for producing contact lenses since they would likely resultin non-homogeneous contact lenses with variable composition andcompromised optical transmittance. Therefore, a need remains for evensimpler methods for producing silicone hydrogel contact lenses withhydrophilic surfaces.

U.S. Pat. No. 4,954,586 describes a process in which silicone hydrogelcontact lenses are treated with alkali solution in a hydrolysis processin order to improve wettability. However, the hydrolysis process isnon-selective and therefore may lead to undesirable degradation ofcertain monomer segments in the contact lens. The hydrolysis could, forexample, lead to destruction of cross-links within the polymer network.For example, difunctional (meth)acrylate esters (e.g., ethylene glycoldimethacrylate, pentaerythritol trimethacrylate, pentaerythritoltetramethacrylate, ethylene glycol diacrylate, pentaerythritoltriacrylate, pentaerythritol tetra-acrylate) are susceptible tohydrolysis in alkali solution. Loss of cross-linking can lead to poormechanical properties, variation in contact lens water content, andcontact lens parameters (diameter, base curve). (Meth)acrylate estersare one of the key building blocks employed in the production ofsilicone hydrogel contact lenses. Difunctional (meth)acrylate esters(e.g., ethylene glycol dimethacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, ethylene glycol diacrylate,pentaerythritol triacrylate, pentaerythritol tetra-acrylate) aresusceptible to hydrolysis in alkali solution. Hydrolysis of esterfunctionality in silicone hydrogel contact lenses can result in theformation of ionic methacrylic acid segments. The presence of ionicfunctionality in silicone hydrogel contact lenses is generallyundesirable since such groups are known to increase the rate of contactlens fouling (e.g., from deposition of protein from tears).

In U.S. Pat. Nos. 8,231,218, 8,552,085, and 9,804,417, Cooper Visiondiscloses the use of hydrophilized poly(dimethyl siloxane) (PDMS) (e.g.,PDMS-di-methacrylate having poly(ethylene glycol) (PEG) groups) as ameans of obtaining silicone hydrogel contact lenses with goodwettability. While this method is an improvement over plasma treatmentof contact lenses, this method also has a number of limitations.PDMS-di-methacrylate having poly(ethylene glycol) (PEG) groups requiresmultiple synthetic sequences, thereby increasing product cost. Inaddition, PEG-containing polymers can be susceptible to degradation,which can cause changes in the properties of an article made from thepoly(oxyalkylene)-containing polymers (US 2007/0195261 and Mantzavinoset al., Chemical Engineering Science, 1996, 51(18), 4219-4235). PEGsegments are prone to oxidative degradation which results in theformation of ocular irritants such as formaldehyde, formic acid andother materials (US 2007/0195261). Air oxidation of PEG generatesunstable peroxides, typical of the auto oxidation of ethers. Theperoxides then react further, leading to cleavage of the PEG chainbetween oxygen and carbon atoms. Therefore, contact lenses containingPEG segments often need to be stabilized with antioxidants. However,many antioxidants (BHT, Hydroquinone, and MEHQ) are known ocularirritants and, while the antioxidants typically slow oxidation, they donot prevent it. A clear need remains for improved technologies to rendersilicone hydrogel contact lenses wettable.

The compositions, devices, and methods described herein address theseand other needs.

SUMMARY

In accordance with the purposes of the disclosed compositions, devices,and methods, as embodied and broadly described herein, the disclosedsubject matter relates to compositions comprisingactinically-crosslinkable polysiloxane-polyglycerol block copolymers,methods of making and use thereof, and devices comprising thecompositions described herein.

More specifically, disclosed herein are compositions comprising anactinically-crosslinkable polysiloxane-polyglycerol block copolymerderived from: a polysiloxane prepolymer comprising a polyglycerol sidechain, the polyglycerol side chain comprising an ethylenicallyunsaturated group covalently linked thereto, wherein the ethylenicallyunsaturated group is actinically curable.

The block copolymers described herein comprise two or more polymericchains (blocks), which are structurally different and chemically bondedto each other. Under certain conditions, these copolymers can segregateinto a variety of ordered structures. In some examples, the orderedblock copolymer structures can be substantially locked in place throughchemical reactions such as cross-linking of actinically curable groups,substitution reactions, and addition reactions, “click” chemicalreactions, polymerization reactions or any number of chemical reactionsknown in the art.

Also described herein are methods of use of the compositions describedherein and articles of manufacture and devices of the compositionsdescribed herein. For example, also described herein are medical devicescomprising of the compositions described herein and the use of suchmedical devices in ophthalmic applications such as contact lenses.

The compositions described herein can be used in the construction ofmedical devices, as coatings for medical devices, and any number ofother biomedical applications. The compositions described herein can, insome examples, be used as hydrophilic coatings for any number of medicaldevices including, but not limited to catheters, contact lenses,endoscopes, cell growth platforms, microfluidic devices, body implants,coatings for implants that come into contact with tissue (e.g.,epithelial tissue, connective tissue, muscle tissue, and nerve tissue)and biological fluids (e.g., blood, mucus, urine, tears, saliva,amniotic fluid, synovial fluid).

Also described herein are ophthalmic devices (e.g., contact lenses,intraocular lenses, corneal inlays, and corneal rings) obtained from theblock copolymers described herein and optionally one or more hydrophilicand/or hydrophobic monomers. The block copolymers and compositionsdescribed herein can, for example, also be used in a range of cellculture applications for the expansion and directed differentiation ofvarious cell types by acting as extracellular matrix mimics for 3D CellCulture. The block copolymers and compositions described herein can, forexample, be used as synthetic matrix metallo-proteinase-sensitivematerials for the conduction of tissue regeneration. The blockcopolymers and compositions described herein can, for example, be usedas micro-valves and micro-pumping devices due to the propensity of thecopolymers and compositions described herein to absorb large volumesaqueous and non-aqueous fluids coupled with the response of thecopolymers and compositions described herein to various forms ofstimulation (examples: pH, electrical current, temperature, ionicstrength).

Additional advantages of the disclosed compositions, devices, andmethods will be set forth in part in the description which follows, andin part will be obvious from the description. The advantages of thedisclosed compositions, devices, and methods will be realized andattained by means of the elements and combinations particularly pointedout in the appended claims. It is to be understood that both theforegoing general description and the following detailed description areexemplary and explanatory only and are not restrictive of the disclosedcompositions and methods, as claimed.

The details of one of more embodiments of the invention are set forth inthe accompanying drawings and description below. Other features,objects, and advantages of the invention will be apparent form thedescription and drawings, and from the claims.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying figures, which are incorporated in and constitute apart of this specification, illustrate several aspects of thedisclosure, and together with the description, serve to explain theprinciples of the disclosure.

FIG. 1 illustrates the self-assembly of PDMS bearing polyglycerolchains.

FIG. 2 illustrates the self-assembly of uni-lamellar AC-PDMS-PGLYvesicles to form a multi-lamellar vesicle.

FIG. 3 illustrates cross-linking of multilamellar AC-PDMS-PGLY.

FIG. 4 is a proton NMR spectrum of a cross-linkablepolysiloxane-polyglycerol block copolymer.

DETAILED DESCRIPTION

The compositions, devices, and methods described herein may beunderstood more readily by reference to the following detaileddescription of specific aspects of the disclosed subject matter and theExamples included herein.

Before the present compositions, devices, and methods are disclosed anddescribed, it is to be understood that the aspects described below arenot limited to specific synthetic methods or specific reagents, as suchmay, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular aspects only andis not intended to be limiting.

Also, throughout this specification, various publications arereferenced. The disclosures of these publications in their entiretiesare hereby incorporated by reference into this application in order tomore fully describe the state of the art to which the disclosed subjectmatter pertains. The references disclosed are also individually andspecifically incorporated by reference herein for the material containedin them that is discussed in the sentence in which the reference isrelied upon.

General Definitions

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings.

Throughout the description and claims of this specification, the word“comprise” and other forms of the word, such as “comprising” and“comprises,” means including but not limited to, and are open,non-limiting terms that are not intended to exclude, for example, otheradditives, components, integers, or steps. Although the terms“comprising” and “including” have been used herein to describe variousexamples, the terms “consisting essentially of” and “consisting of” canbe used in place of “comprising” and “including” to provide for morespecific examples of the invention and are also disclosed. Other than inthe examples, or where otherwise noted, all numbers expressingquantities of ingredients, reaction conditions, and so forth used in thespecification and claims are to be understood at the very least, and notas an attempt to limit the application of the doctrine of equivalents tothe scope of the claims, to be construed in light of the number ofsignificant digits and ordinary rounding approaches.

“Exemplary” means “an example of” and is not intended to convey anindication of a preferred or ideal embodiment. “Such as” is not used ina restrictive sense, but for explanatory purposes.

As used in the description and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. This, for example, reference to “a composition”includes mixtures of two or more such compositions, reference to “thecompound” includes mixtures of two or more such compounds, reference to“an agent” includes mixtures of two or more such agents, and the like.

“Optional” or “optionally” means that the subsequently described eventor circumstance occurs and instances where it does not.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. By “about” is meant within5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such arange is expressed, another aspect includes from the one particularvalue and/or to the other particular value. Similarly, when values areexpressed as approximations, by use of the antecedent “about,” it willbe understood that the particular value forms another aspect. It will befurther understood that the endpoints of each of the ranges aresignificant both in relation to the other endpoint, and independently ofthe other endpoint.

It is understood that throughout this specification the identifiers“first” and “second” are used solely to aid in distinguishing thevarious components and steps of the disclosed subject matter. Theidentifiers “first” and “second” are not intended to imply anyparticular order, amount, preference, or importance to the components orsteps modified by these terms.

Chemical Definitions

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs.

The organic moieties mentioned when defining variable positions withinthe general formulae described herein (e.g., the term “halogen”) arecollective terms for the individual substituents encompassed by theorganic moiety. The prefix C_(n)-C_(m) preceding a group or moietyindicates, in each case, the possible number of carbon atoms in thegroup or moiety that follows.

References in the specification and concluding claims to parts by weightof a particular element or component in a composition denotes the weightrelationship between the element or component and any other elements orcomponents in the composition or article for which a part by weight isexpressed. Thus, in a compound containing 2 parts by weight of componentX and 5 parts by weight component Y, X and Y are present at a weightratio of 2:5, and are present in such ratio regardless of whetheradditional components are contained in the compound.

A weight percent (wt. %) of a component, unless specifically stated tothe contrary, is based on the total weight of the formulation orcomposition in which the component is included.

The term “ion,” as used herein, refers to any molecule, portion of amolecule, cluster of molecules, molecular complex, moiety, or atom thatcontains a charge (positive, negative, or both at the same time withinone molecule, cluster of molecules, molecular complex, or moiety (e.g.,zwitterions)) or that can be made to contain a charge. Methods forproducing a charge in a molecule, portion of a molecule, cluster ofmolecules, molecular complex, moiety, or atom are disclosed herein andcan be accomplished by methods known in the art, e.g., protonation,deprotonation, oxidation, reduction, alkylation, acetylation,esterification, de-esterification, hydrolysis, etc.

The term “anion” is a type of ion and is included within the meaning ofthe term “ion.” An “anion” is any molecule, portion of a molecule (e.g.,zwitterion), cluster of molecules, molecular complex, moiety, or atomthat contains a net negative charge or that can be made to contain a netnegative charge. The term “anion precursor” is used herein tospecifically refer to a molecule that can be converted to an anion via achemical reaction (e.g., deprotonation).

The term “cation” is a type of ion and is included within the meaning ofthe term “ion.” A “cation” is any molecule, portion of a molecule (e.g.,zwitterion), cluster of molecules, molecular complex, moiety, or atom,that contains a net positive charge or that can be made to contain a netpositive charge. The term “cation precursor” is used herein tospecifically refer to a molecule that can be converted to a cation via achemical reaction (e.g., protonation or alkylation).

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, and aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described below. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this disclosure, the heteroatoms, such as nitrogen, canhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valencies of theheteroatoms. This disclosure is not intended to be limited in any mannerby the permissible substituents of organic compounds. Also, the terms“substitution” or “substituted with” include the implicit proviso thatsuch substitution is in accordance with permitted valence of thesubstituted atom and the substituent, and that the substitution resultsin a stable compound, e.g., a compound that does not spontaneouslyundergo transformation such as by rearrangement, cyclization,elimination, etc.

“Z¹,” “Z²,” “Z³,” and “Z⁴” are used herein as generic symbols torepresent various specific substituents. These symbols can be anysubstituent, not limited to those disclosed herein, and when they aredefined to be certain substituents in one instance, they can, in anotherinstance, be defined as some other substituents.

The term “aliphatic” as used herein refers to a non-aromatic hydrocarbongroup and includes branched and unbranched, alkyl, alkenyl, or alkynylgroups.

As used herein, the term “alkyl” refers to saturated, straight-chainedor branched saturated hydrocarbon moieties. Unless otherwise specified,C₁-C₂₄ (e.g., C₁-C₂₂, C₁-C₂₀, C₁-C₁₈, C₁-C₁₆, C₁-C₁₄, C₁-C₁₂, C₁-C₁₀,C₁-C₈, C₁-C₆, or C₁-C₄) alkyl groups are intended. Examples of alkylgroups include methyl, ethyl, propyl, 1-methyl-ethyl, butyl,1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, pentyl,1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethyl-propyl,1-ethyl-propyl, hexyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl,1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl,1,1-dimethyl-butyl, 1,2-dimethyl-butyl, 1,3-dimethyl-butyl,2,2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl,1-ethyl-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl,1,2,2-trimethyl-propyl, 1-ethyl-1-methyl-propyl,1-ethyl-2-methyl-propyl, heptyl, octyl, nonyl, decyl, dodecyl,tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Alkylsubstituents may be unsubstituted or substituted with one or morechemical moieties. The alkyl group can be substituted with one or moregroups including, but not limited to, hydroxyl, halogen, acyl, alkyl,alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, cyano,carboxylic acid, ester, ether, ketone, nitro, phosphonyl, silyl,sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below,provided that the substituents are sterically compatible and the rulesof chemical bonding and strain energy are satisfied.

Throughout the specification “alkyl” is generally used to refer to bothunsubstituted alkyl groups and substituted alkyl groups; however,substituted alkyl groups are also specifically referred to herein byidentifying the specific substituent(s) on the alkyl group. For example,the term “halogenated alkyl” specifically refers to an alkyl group thatis substituted with one or more halides (halogens; e.g., fluorine,chlorine, bromine, or iodine). The term “alkoxyalkyl” specificallyrefers to an alkyl group that is substituted with one or more alkoxygroups, as described below. The term “alkylamino” specifically refers toan alkyl group that is substituted with one or more amino groups, asdescribed below, and the like. When “alkyl” is used in one instance anda specific term such as “alkylalcohol” is used in another, it is notmeant to imply that the term “alkyl” does not also refer to specificterms such as “alkylalcohol” and the like.

This practice is also used for other groups described herein. That is,while a term such as “cycloalkyl” refers to both unsubstituted andsubstituted cycloalkyl moieties, the substituted moieties can, inaddition, be specifically identified herein; for example, a particularsubstituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.” Similarly, a substituted alkoxy can be specificallyreferred to as, e.g., a “halogenated alkoxy,” a particular substitutedalkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, thepractice of using a general term, such as “cycloalkyl,” and a specificterm, such as “alkylcycloalkyl,” is not meant to imply that the generalterm does not also include the specific term.

As used herein, the term “alkenyl” refers to unsaturated,straight-chained, or branched hydrocarbon moieties containing a doublebond. Unless otherwise specified, C₂-C₂₄ (e.g., C₂-C₂₂, C₂-C₂₀, C₂-C₁₈,C₂-C₁₆, C₂-C₁₄, C₂-C₁₂, C₂-C₁₀, C₂-C₈, C₂-C₆, or C₂-C₄) alkenyl groupsare intended. Alkenyl groups may contain more than one unsaturated bond.Examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl,1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl,2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl,2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl,2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl,1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl,5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl,3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl,1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl,3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and1-ethyl-2-methyl-2-propenyl. The term “vinyl” refers to a group havingthe structure —CH═CH₂; 1-propenyl refers to a group with the structure—CH═CH—CH₃; and 2-propenyl refers to a group with the structure—CH₂—CH═CH₂. Asymmetric structures such as (Z¹Z²)C═C(Z³Z⁴) are intendedto include both the E and Z isomers. This can be presumed in structuralformulae herein wherein an asymmetric alkene is present, or it can beexplicitly indicated by the bond symbol C═C. Alkenyl substituents may beunsubstituted or substituted with one or more chemical moieties.Examples of suitable substituents include, for example, alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, cyano,carboxylic acid, ester, ether, halide, hydroxyl, ketone, nitro,phosphonyl, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, asdescribed below, provided that the substituents are stericallycompatible and the rules of chemical bonding and strain energy aresatisfied.

As used herein, the term “alkynyl” represents straight-chained orbranched hydrocarbon moieties containing a triple bond. Unless otherwisespecified, C₂-C₂₄ (e.g., C₂-C₂₄, C₂-C₂₀, C₂-C₁₈, C₂-C₁₆, C₂-C₁₄, C₂-C₁₂,C₂-C₁₀, C₂-C₈, C₂-C₆, or C₂-C₄) alkynyl groups are intended. Alkynylgroups may contain more than one unsaturated bond. Examples includeC₂-C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl),1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-1-butynyl,1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl,4-methyl-1-pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl,1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl-4-pentynyl,2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl, and 1-ethyl-1-methyl-2-propynyl. Alkynyl substituentsmay be unsubstituted or substituted with one or more chemical moieties.Examples of suitable substituents include, for example, alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, acyl, aldehyde, amino, cyano,carboxylic acid, ester, ether, halide, hydroxyl, ketone, nitro,phosphonyl, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, asdescribed below.

As used herein, the term “aryl,” as well as derivative terms such asaryloxy, refers to groups that include a monovalent aromatic carbocyclicgroup of from 3 to 50 carbon atoms. Aryl groups can include a singlering or multiple condensed rings. In some embodiments, aryl groupsinclude C₆-C₁₀ aryl groups. Examples of aryl groups include, but are notlimited to, benzene, phenyl, biphenyl, naphthyl, tetrahydronaphthyl,phenylcyclopropyl, phenoxybenzene, and indanyl. The term “aryl” alsoincludes “heteroaryl,” which is defined as a group that contains anaromatic group that has at least one heteroatom incorporated within thering of the aromatic group. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, sulfur, and phosphorus. The term“non-heteroaryl,” which is also included in the term “aryl,” defines agroup that contains an aromatic group that does not contain aheteroatom. The aryl substituents may be unsubstituted or substitutedwith one or more chemical moieties. Examples of suitable substituentsinclude, for example, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl,acyl, aldehyde, amino, cyano, carboxylic acid, ester, ether, halide,hydroxyl, ketone, nitro, phosphonyl, silyl, sulfo-oxo, sulfonyl,sulfone, sulfoxide, or thiol as described herein. The term “biaryl” is aspecific type of aryl group and is included in the definition of aryl.Biaryl refers to two aryl groups that are bound together via a fusedring structure, as in naphthalene, or are attached via one or morecarbon-carbon bonds, as in biphenyl.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ringcomposed of at least three carbon atoms. Examples of cycloalkyl groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, etc. The term “heterocycloalkyl” is a cycloalkyl group asdefined above where at least one of the carbon atoms of the ring issubstituted with a heteroatom such as, but not limited to, nitrogen,oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkylgroup can be substituted or unsubstituted. The cycloalkyl group andheterocycloalkyl group can be substituted with one or more groupsincluding, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, acyl, aldehyde, amino, cyano, carboxylic acid, ester, ether,halide, hydroxyl, ketone, nitro, phosphonyl, silyl, sulfo-oxo, sulfonyl,sulfone, sulfoxide, or thiol as described herein.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-basedring composed of at least three carbon atoms and containing at least onedouble bound, i.e., C═C. Examples of cycloalkenyl groups include, butare not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like. The term“heterocycloalkenyl” is a type of cycloalkenyl group as defined aboveand is included within the meaning of the term “cycloalkenyl,” where atleast one of the carbon atoms of the ring is substituted with aheteroatom such as, but not limited to, nitrogen, oxygen, sulfur, orphosphorus. The cycloalkenyl group and heterocycloalkenyl group can besubstituted or unsubstituted. The cycloalkenyl group andheterocycloalkenyl group can be substituted with one or more groupsincluding, but not limited to, alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, acyl, aldehyde, amino, cyano, carboxylic acid, ester, ether,halide, hydroxyl, ketone, nitro, phosphonyl, silyl, sulfo-oxo, sulfonyl,sulfone, sulfoxide, or thiol as described herein.

The term “cyclic group” is used herein to refer to either aryl groups,non-aryl groups (i.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, andheterocycloalkenyl groups), or both. Cyclic groups have one or more ringsystems that can be substituted or unsubstituted. A cyclic group cancontain one or more aryl groups, one or more non-aryl groups, or one ormore aryl groups and one or more non-aryl groups.

The term “acyl” as used herein is represented by the formula —C(O)Z¹where Z¹ can be a hydrogen, hydroxyl, alkoxy, alkyl, alkenyl, alkynyl,aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, orheterocycloalkenyl group described above. As used herein, the term“acyl” can be used interchangeably with “carbonyl.” Throughout thisspecification “C(O)” or “CO” is a shorthand notation for C═O.

The term “acetal” as used herein is represented by the formula(Z¹Z²)C(═OZ³)(═OZ⁴), where Z¹, Z², Z³, and Z⁴ can be, independently, ahydrogen, halogen, hydroxyl, alkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl groupdescribed above.

The term “alkanol” as used herein is represented by the formula Z¹OH,where Z¹ can be an alkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl groupdescribed above.

As used herein, the term “alkoxy” as used herein is an alkyl group boundthrough a single, terminal ether linkage; that is, an “alkoxy” group canbe defined as to a group of the formula Z¹—O—, where Z¹ is unsubstitutedor substituted alkyl as defined above. Unless otherwise specified,alkoxy groups wherein Z¹ is a C₁-C₂₄ (e.g., C₁-C₂₂, C₁-C₂₀, C₁-C₁₈,C₁-C₁₆, C₁-C₁₄, C₁-C₁₂, C₁-C₁₀, C₁-C₈, C₁-C₆, or C₁-C₄) alkyl group areintended. Examples include methoxy, ethoxy, propoxy, 1-methyl-ethoxy,butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1,1-dimethyl-ethoxy,pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy,2,2-di-methyl-propoxy, 1-ethyl-propoxy, hexoxy, 1,1-dimethyl-propoxy,1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl-pentoxy,3-methyl-pentoxy, 4-methyl-penoxy, 1,1-dimethyl-butoxy,1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy,2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy,1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy,1-ethyl-1-methyl-propoxy, and 1-ethyl-2-methyl-propoxy.

The term “aldehyde” as used herein is represented by the formula —C(O)H.Throughout this specification “C(O)” is a shorthand notation for C═O.

The terms “amine” or “amino” as used herein are represented by theformula —NZ¹Z²Z³, where Z¹, Z², and Z³ can each be substitution group asdescribed herein, such as hydrogen, an alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, orheterocycloalkenyl group described above.

The terms “amide” or “amido” as used herein are represented by theformula —C(O)NZ¹Z², where Z¹ and Z² can each be substitution group asdescribed herein, such as hydrogen, an alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, orheterocycloalkenyl group described above.

The term “anhydride” as used herein is represented by the formulaZ¹C(O)OC(O)Z² where Z¹ and Z², independently, can be an alkyl, alkenyl,alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl,or heterocycloalkenyl group described above.

The term “cyclic anhydride” as used herein is represented by theformula:

where Z¹ can be an alkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl groupdescribed above.

The term “azide” as used herein is represented by the formula —N═N═N.

The term “carboxylic acid” as used herein is represented by the formula—C(O)OH.

A “carboxylate” or “carboxyl” group as used herein is represented by theformula —C(O)O⁻¹.

The term “cyano” as used herein is represented by the formula —CN.

The term “ester” as used herein is represented by the formula —OC(O)Z¹or —C(O)OZ¹, where Z¹ can be an alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, orheterocycloalkenyl group described above.

The term “ether” as used herein is represented by the formula Z¹OZ²,where Z¹ and Z² can be, independently, an alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, orheterocycloalkenyl group described above.

The term “epoxy” or “epoxide” as used herein refers to a cyclic etherwith a three atom ring and can represented by the formula:

where Z¹, Z², Z³, and Z⁴ can be, independently, an alkyl, alkenyl,alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl,or heterocycloalkenyl group described above.

The term “ketone” as used herein is represented by the formula Z¹C(O)Z²,where Z¹ and Z² can be, independently, an alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, orheterocycloalkenyl group described above.

The term “halide” or “halogen” or “halo” as used herein refers tofluorine, chlorine, bromine, and iodine.

The term “hydroxyl” as used herein is represented by the formula —OH.

The term “nitro” as used herein is represented by the formula —NO₂.

The term “perfluoro” is used herein as a prefix to indicate most or allC—H bonds in the compound following the prefix have been replaced by C—Fbonds, as allowed under steric and stability constraints. For example,in the case of fluorinated (meth)acrylates, the compounds are notcompletely fluorinated due to instability. The —OCF₂— group inR—C(═CH₂)—C(═O)—OCF₂—(CF₂)_(n)—CF₃ is unstable, butR—C(═CH₂)—C(═O)—OCH₂—(CF₂)_(n)—CF₃ is stable (where R═H is an acrylateand R═CH₃ is a methacrylate). Similarly, the HOCF₂— group inHO—CF₂(CF₂)_(n)—CF₃ is unstable, but HO—CH₂—(CF₂)_(n)—CF₃ is stable.Therefore the alcohols with the general structure HO—CH₂(CF₂)_(n)—CF₃can be used in the synthesis of (meth)acrylates with highly fluorinatedside chains. (Meth)acrylates with highly fluorinated side chains areavailable commercially.

Examples of (meth)acrylates with highly fluorinated side chains include,but are not limited to 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-heptylacrylate;3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluoro-dodecylacrylate; 2,2,3,3,4,4,4,-heptafluorobutyl (meth)acrylate;1,1,1,3,3,3-hexafluoroisopropyl methacrylate; and2,2,3,3,4,4,5,5-octafluoropentyl methacrylate. A perfluorinatedpolyether can be synthesized using a perfluorinated initiator M⁺B⁻, suchas Na⁺OCF₃ ⁻, as shown below in Scheme 1.

The term “phosphonyl” is used herein to refer to the phospho-oxo grouprepresented by the formula —P(O)(OZ¹)₂, where Z¹ can be hydrogen, analkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,heterocycloalkyl, or heterocycloalkenyl group described above.

The term “silyl” as used herein is represented by the formula —SiZ¹Z²Z³,where Z¹, Z², and Z³ can be, independently, hydrogen, alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,heterocycloalkyl, or heterocycloalkenyl group described above.

The term “sulfonyl” or “sulfone” is used herein to refer to thesulfo-oxo group represented by the formula —S(O)₂Z¹, where Z¹ can behydrogen, an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl,cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group describedabove.

The term “sulfide” as used herein is comprises the formula —S—.

The term “thiol” as used herein is represented by the formula —SH.

“R¹,” “R²,” “R³,” “R^(n),” etc., where n is some integer, as used hereincan, independently, possess one or more of the groups listed above. Forexample, if R¹ is a straight chain alkyl group, one of the hydrogenatoms of the alkyl group can optionally be substituted with a hydroxylgroup, an alkoxy group, an amine group, an alkyl group, a halide, andthe like. Depending upon the groups that are selected, a first group canbe incorporated within second group or, alternatively, the first groupcan be pendant (i.e., attached) to the second group. For example, withthe phrase “an alkyl group comprising an amino group,” the amino groupcan be incorporated within the backbone of the alkyl group.Alternatively, the amino group can be attached to the backbone of thealkyl group. The nature of the group(s) that is (are) selected willdetermine if the first group is embedded or attached to the secondgroup.

Unless stated to the contrary, a formula with chemical bonds shown onlyas solid lines and not as wedges or dashed lines contemplates eachpossible stereoisomer or mixture of stereoisomer (e.g., each enantiomer,each diastereomer, each meso compound, a racemic mixture, or scalemicmixture).

As used herein, by a “subject” is meant an individual. Thus, the“subject” can include domesticated animals (e.g., cats, dogs, etc.),livestock (e.g., cattle, horses, pigs, sheep, goats, etc.), laboratoryanimals (e.g., mouse, rabbit, rat, guinea pig, etc.), and birds.“Subject” can also include a mammal, such as a primate or a human.

An “ophthalmic device”, as used herein, refers to any of the following:a contact lens (hard or soft), an intraocular lens, a corneal inlay,glaucoma shunt, or ophthalmic stent used on or about a subject's eye orocular vicinity.

“Contact Lens” refers to a structure that can be placed on or within asubject's eye. A contact lens can correct, improve, or alter a subject'seyesight. However, a contact lens may also be used as an eye bandage,drug delivery device, and prosthetic device. In the case of colorcontact lenses, the device may be used to alter or enhance a subject'seye color, or to mask a subject's disfigured eyes. A contact lens can beof any appropriate material, and can be a soft lens, a hard lens, or ahybrid lens.

A “silicone hydrogel contact lens” refers to a contact lens comprising asilicone hydrogel material.

“Hydrophilic,” as used herein, describes a material or portion thereofthat has the characteristics of readily absorbing or dissolving inwater, having polar groups (distribution of electrons is uneven,enabling it to take part in electrostatic interactions) that readilyinteract with water, and/or having an affinity for water.

As used herein, the term “hydrophobic” refers to the characteristics ofnot readily absorbing or dissolving in water, being adversely affectedby water, and/or having little or no affinity for water.

As used herein, the term “amphiphilic” refers to the characteristics ofhaving both hydrophilic and hydrophobic properties.

As used herein, the term “hydrophilic-lipophilic balance” (HLB) of asurfactant is a measure of the degree to which it is hydrophilic orlipophilic. The HLB for a substance is determined by calculating valuesfor the different regions of the molecule, as described by Griffin(Griffin. J. Soc. Cosm. Chem. 1954, 5, 249-256). Other methods fordetermining HLB have been suggested, notably in 1957 by Davies (Davies,Proceedings of the International Congress of Surface Activity,Gas/Liquid and Liquid/Liquid Interface, 1957, 426-3); HLB according toDavies is intended to mean the equilibrium between the size and thestrength of the hydrophilic group and the size and the strength of thelipophilic group of the surfactant under consideration.

A “hydrogel” or “hydrogel material” refers to a polymeric material whichcan absorb 10% by weight of water or more when it is fully hydrated(e.g., 15% or more, 20% or more, 25% or more, 30% or more, 40% or more,50% or more, 60% or more, 70% or more, 80% or more, or 90% or more).

A “silicone hydrogel” refers to a siloxane or silicone-containinghydrogel obtained by copolymerization of a polymerizable compositioncomprising at least one silicone-containing monomer, at least onesilicone-containing macromer, or at least one crosslinkablesilicone-containing prepolymer.

A “vinylic monomer” means a low molecular weight compound having oneethylenically unsaturated group. Low molecular weight typically meansaverage molecular weights less than 600 Daltons. Vinyl group asdescribed here includes, but is not limited to, the following functionalgroups: alkene, (meth)acrylate, (meth)acrylamide, and styrenicfunctionality.

A “silicone-containing vinylic monomer” refers to a vinylic monomerwhich contains silicone.

A “hydrophilic vinylic monomer” refers to a vinylic monomer which can bepolymerized actinically to form a polymer that is water-soluble or canabsorb 20% by weight of water or more (e.g., 30% or more, 40% or more,50% or more, 60% or more, 70% or more, 80% or more, or 90% or more).

A “hydrophobic vinylic monomer” refers to a vinylic monomer which can bepolymerized actinically (or thermally) to form a polymer that isinsoluble in water and can absorb less than 20% by weight water (e.g.,15% or less, 10% or less, 5% or less, or 1% or less).

The term “olefinically unsaturated group” or “ethylenically unsaturatedgroup” is employed herein in a broad sense and is intended to encompassany groups containing a carbon-carbon double bonded group (>C═C< group).Exemplary ethylenically unsaturated groups include, but are not limitedto, (meth)acrylamide, (meth)acryloyl, allyl, vinyl, styrenyl, orother >C═C< containing groups.

“Polymer” means a material formed by polymerizing one or more monomers.

The term “(co)polymer” includes homopolymers, copolymers, or mixturesthereof.

The term “(meth)acryl . . . ” includes “acryl . . . ,” “methacryl . . .,” or mixtures thereof.

The term “block copolymer” as used herein is a copolymer comprised oftwo or more homopolymer subunits linked by covalent bonds. The joiningof the homopolymer subunits may require an intermediate non-repeatingsubunit, known as a junction block. Block copolymers with two or threedistinct blocks are called di-block copolymers and tri-block copolymers,respectively. A block is a portion of a macromolecule, comprising manyconstitutional units, that has at least one feature which is not presentin the adjacent portions.

The term prepolymer is used herein to refer to a polymer that hasreactive groups that are available for bond forming reactions that willcrosslink (intermolecular and/or intramolecular crosslink). It is notmeant to imply that the prepolymer is not yet a polymer (e.g., a monomeror polymer precursor). Rather, a “prepolymer” refers to a startingpolymer which contains multiple actinically crosslinkable groups and canbe cured (e.g., crosslinked) actinically to obtain a crosslinked polymerhaving a molecular weight higher than the starting polymer.

A “silicone-containing prepolymer” refers to a prepolymer which containssilicone and can be crosslinked actinically (or with heat) to obtain acrosslinked polymer having a molecular weight higher than the startingpolymer.

“Molecular weight” of a polymeric material (including monomeric ormacro-monomeric materials), as used herein, refers to the number-averagemolecular weight unless otherwise specifically noted or unless testingconditions indicate otherwise.

A “macromer” refers to a medium and high molecular weight compound whichcan be polymerized and/or crosslinked actinically. Medium and highmolecular weight typically means average molecular weights greater than600 Daltons. For example, a macromer can be a macromer with one or moreethylenically unsaturated groups. A “siloxane-containing macromer” is amacromer which contains silicone and can be crosslinked actinically orwith heat.

The term “hyper-branched polyglycerol” as used herein refers to abranched aliphatic polyether with hydroxyl groups. It will beappreciated that the term also includes a branched polyether in which aproportion of the hydroxyl groups have been derivatized and/or replacedwith a suitable group. Examples of hyper-branched polyglycerolstructures are illustrated by Formula III, Formula IV, Formula V,Formula VI, Formula VII, Formula VIII, and Formula IX.

As used herein, the term “multiple” refers to at least two, preferablyat least three.

As used herein, “actinically” in reference to curing, crosslinking, orpolymerizing of a polymerizable composition, a prepolymer, or a materialmeans that the curing (e.g., crosslinking and/or polymerizing) isperformed by actinic irradiation, such as, for example, UV light,visible light, ionized radiation (e.g., gamma ray or X-ray irradiation),microwave radiation, and the like. Thermal curing or actinic curingmethods are well-known in the art.

A “photo-initiator” refers to a chemical that initiates radicalcrosslinking/polymerizing reaction by the use of light.

A “thermal initiator” refers to a chemical that initiates free radicalpolymerization and/or cross-linking reactions using heat energy.

The term “fluid” as used herein indicates that a material is capable offlowing like a liquid. Fluids include, for example, liquids, gases,supercritical fluids, etc.

The term “genetic material” as used herein includes DNA, RNA, modifiedDNA and modified RNA.

The term “vesicle” as used herein refers to a synthetic or naturaltube-like structure capable of being filled with a fluid. The vesiclesmay provide efficient mass transport for fluids by acting as conduitsfor the fluids. The vesicle tube walls may be hydrophilic orhydrophobic. Vesicles may coalesce with other vesicles to form morecomplex structures.

The term “chemical stability” as used herein is defined by substantialmaintenance of chemical bonds in a particular structure.

The term “biological materials” includes, for example, cells, yeasts,bacteria, proteins, peptides, cytokines, and hormones. Cells includeprogenitor cells (e.g., endothelial progenitor cells), stem cells (e.g.,mesenchymal, hematopoietic, neuronal), stromal cells, parenchymal cells,undifferentiated cells, fibroblasts, macrophage, and satellite cells.

Epithelial tissue covers or lines all body surfaces inside or outsidethe body of a subject. Examples of epithelial tissue include, but arenot limited to, the skin, epithelium, dermis, and the mucosa and serosathat line the body cavity and internal organs (such as the heart, lung,liver, kidney, intestines, bladder, uterus, etc.).

Connective tissue is the most abundant and widely distributed of alltissues. Examples of connective tissue include, but are not limited to,vascular tissue (e.g., arteries, veins, and capillaries), blood (e.g.,red blood cells, platelets, and white blood cells), lymph, fat, fibers,cartilage, ligaments, tendon, bone, teeth, omentum, peritoneum,mesentery, meniscus, conjunctiva, dura mater, umbilical cord, etc.

Muscle tissue accounts for nearly one-third of the total body weight ofa human subject. There are three distinct subtypes of muscle tissue:striated (skeletal) muscle, smooth (visceral) muscle, and cardiacmuscle. Examples of muscle tissue include, but are not limited to,myocardium (heart muscle), skeletal, intestinal wall, etc.

The fourth primary type of tissue is nerve tissue. Nerve tissue is foundin the brain, spinal cord, and accompanying nerves. Nerve tissue iscomposed of specialized cells called neurons (nerve cells) andneuroglial or glial cells.

“Anti-thrombotic” as used herein refers to a medical device that hasreduced ability to cause a blood clot and/or a reduced rated ofclotting, as compared to an untreated medical device. It will beappreciated that the reduced clotting associated with the device is notto be limited to clots that form within the device, but also includesother clots associated with the use of the device.

The term “click chemistry” as used herein refers to a group of reactionsthat are versatile, fast, high yielding, highly selective (e.g.regio-selectivity and stereo selectivity) and allow targeted structuresto be produced under conditions that allow for straightforward isolationand purification of reaction products. The term “click chemistry” wasintroduced by K. Barry Sharpless, Hartmuth Kolb, and M. G. Finn of TheScripps Research Institute in 2001 (Kolb et al. Angewandte ChemieInternational Edition. 2001, 40(11), 2004-2021; Evans. AustralianJournal of Chemistry. 2007, 60(6), 384-395).

Examples of click chemical reactions include: Huisgen 1,3-dipolarcycloaddition of alkynes to azides to form1,4-disubstituted-1,2,3-triazoles; thiol-ene reactions, (also alkenehydrothiolation)—an organic reaction between a thiol and an alkene toform an alkyl sulfide; nucleophilic ring-opening reactions, which referto the openings of strained heterocyclic electrophiles, such asaziridines, epoxides, cyclic sulfates, aziridinium ions, andepisulfonium ions; Thiol-Isocyanate reactions, such as base catalyzedthiol-isocyanate anionic reactions; and N-hydroxysuccinimide (NHS)activated ester reactions with amino groups.

Chain Extension reactions, as used herein in reference topolysiloxane-co-polyglycerol (branched) copolymers, is intended todescribe a process in which one or morepolydimethylsiloxane-polyglycerol (PDMS-PGLY) copolymer units areconnected without formation of a cross-linked network.

The term “chain extender,” as used herein in reference topolydimethylsiloxane-co-polyglycerol copolymers is intended to describedi-functional substances capable of connectingpolydimethylsiloxane-co-polyglycerol copolymer units without formationof a cross-linked network.

Gelation as used herein refers to a stage in a chemical reaction atwhich a polymer is no longer able to flow. In a theoretical sense,gelation is characterized by interconnected polymers chains (NetworkStructure) forming an infinitely large molecule which is not able toflow. Cross-linking reactions can continue to occur beyond the point ofgelation, thereby increasing the degree of rigidity of the polymernetwork.

Handling tint in reference to a contact lens means a lightly tintedcontact lens. This is accomplished by dying (or coloring) of a lens toenable the subject to easily locate a contact lens in a clear solutionwithin a lens storage container, disinfecting container, or cleaningcontainer. A dye and/or a pigment can be used in visibility tinting of acontact lens.

“Dye” means a substance that is soluble in a solvent and that is used toimpart color. Dyes are typically translucent and absorb but do notscatter light. Any suitable biocompatible dye can be used in the presentinvention.

A “pigment” refers to a powdered substance that is suspended in a liquidin which it is insoluble. A pigment can be a conventional pigment,fluorescent pigment, phosphorescent pigment, or pearlescent pigment. Anysuitable pigment may be employed. In some examples, the pigment is heatresistant, non-toxic, and insoluble in aqueous solutions.

“Surface modification”, as used herein, means that an article has beentreated in a surface treatment process (or a surface modificationprocess) prior to or posterior to the formation of the article, in which(1) a coating is applied to the surface of the article, (2) chemicalspecies are adsorbed onto the surface of the article, (3) the chemicalnature (e.g., electrostatic charge) of chemical groups on the surface ofthe article are altered, or (4) the surface properties of the articleare otherwise modified. Exemplary surface treatment processes include,but are not limited to, corona, UV-ozone, and plasma processes in whichan ionized gas is applied to the surface of an article (see, forexample, U.S. Pat. Nos. 4,312,575 and 4,632,844); a surface treatment byenergy other than plasma (e.g., a static electrical charge, irradiation,or other energy source); chemical treatments; the grafting ofhydrophilic monomers or macromers onto the surface of an article;mold-transfer coating processes such as those described in U.S. Pat. No.6,719,929; the incorporation of wetting agents into a lens formulationfor making contact lenses (i.e., surface treatment prior topolymerization), such as those described in U.S. Pat. Nos. 4,045,547,4,042,552, 5,198,477, 5,219,965, 6,367,929, 6,822,016, and 7,279,507;and layer-by-layer coating (“LBL coating”) obtained, for exampleaccording to methods described in U.S. Pat. Nos. 6,451,871, 6,719,929,6,793,973, 6,811,805, and 6,896,926.

“Post-curing surface treatment,” as used herein in reference to asilicone hydrogel material or a soft contact lens, means a surfacetreatment process that is performed after the formation (curing) of thehydrogel material or the soft contact lens in a mold.

A “hydrophilic surface,” as used herein in reference to a siliconehydrogel material or a contact lens, means that the silicone hydrogelmaterial or the contact lens has a surface hydrophilicity characterizedby having an average water contact angle of 90 degrees or less (e.g., 80degrees or less, 70 degrees or less, 60 degrees or less, 50 degrees orless, 40 degrees or less, 30 degrees or less, 20 degrees or less, or 10degrees or less). Contact angle can be measured by a sessile drop methodusing advancing angle or using a captive bubble method. The averagecontact angle using sessile drop method refers to a water contact angleobtained by averaging the measurements of at least 3 individual contactlenses. The captive bubble (sessile bubble) method is a specialarrangement for measuring the contact angle between a liquid and a solidusing drop shape analysis. Instead of placing a drop on the solid as inthe case of the sessile drop, a bubble of air is injected beneath asolid, the surface of which is located in the liquid. Unless otherwisenoted, contact angles for materials of the present invention correspondto a captive bubble contact angle measurement.

An “antimicrobial agent”, as used herein, refers to an agent that iscapable of decreasing, eliminating, or inhibiting the growth ofmicroorganisms.

“Antimicrobial compound” as used herein, refers to organic compoundswith functional groups known for antimicrobial activity. Functionalgroups known for antimicrobial activity include, but are not limited to,quaternary ammonium, chalcones, quinolones, phenolics, polyphenols,phenolic acids, quinones, saponins, flavonoids, tannins, coumarins,terpenoids, alkaloids. Example antimicrobial compounds include, but arenot limited to, substituted polycationic polysiloxane cationicanthraquinone-based dye and Poly(hexamethylenebiguanide) hydrochloride.

“Antimicrobial metals” are metals whose ions have an antimicrobialeffect and which are biocompatible. In some examples, the antimicrobialmetal comprises Ag, Au, Pt, Pd, Ir, Sn, Cu, Sb, Bi, or Zn. In someexamples, the antimicrobial metal comprises Ag.

“Antimicrobial metal-containing nanoparticles” refer to particles havinga size of less than 1 micrometer and containing at least oneantimicrobial metal present in one or more of its oxidation states.“Antimicrobial metal nanoparticles” refer to particles which consistessentially of an antimicrobial metal and have a size of less than 1micrometer. The antimicrobial metal in the antimicrobial metalnanoparticles can be present in one or more of its oxidation states. Forexample, silver-containing nanoparticles can contain silver in one ormore of its oxidation states, such as Ag⁰, Ag¹⁺, and Ag²⁺.

“Oxygen permeability” of a contact lens is abbreviated as Dk where “D”is diffusivity (cm²/sec) and “k” is the solubility of oxygen in a givencontact lens material (ml O²/ml of material×mm Hg). Oxygen permeability,Dk, is conveniently expressed in units of barrers, where “barrer” isdefined at standard temperature and pressure (STP) as: barrer=10⁻¹¹(mLO₂·cm)/(sec·cm²·mm Hg). Oxygen transmissibility (Dk/t) takes intoaccount the thickness (t) of the contact lens and has the unit's mLO₂/(sec·cm²·mm Hg).

The “oxygen transmissibility” of a contact lens, as used herein, is therate at which oxygen will pass through a specific contact lens. Herein,a polarographic method was used to measures oxygen transmissibility(Dk/t) of contact lenses. In this method, Dk/t is measured by detectingthe amount of electrical current produced between the two dissimilarmetals of the polarographic cell (gold & silver) via an electrolyte(saline). Equation 1 below shows the chemical equation for the reductionof dissolved oxygen in water. Equation 1 shows that electrochemicalreduction of one oxygen molecule in saline consumes 4 electrons andproduces 4 hydroxide ions. In this process, hydroxide ions migratethrough the electrolyte to the anode thereby generating an electriccurrent. The amount of electrical current that is produced isproportional to the amount of oxygen available at the interface of thesample and polarographic cell.O₂±2H₂+4e ⁻→4HO⁻  (1)

The electric current associated with the electrochemical reduction ofoxygen in saline can be represented by Equation 2.

$\begin{matrix}{\frac{Dk_{apparent}}{t_{ave}} = {\frac{I}{{nFA}\Delta P} = {BI}}} & (2)\end{matrix}$Equation 2 is the relationship between the Apparent OxygenTransmissibility (AOT, Dk_(apparent)/t_(ave)), electric current (I),cell constant (B), and average lens thickness were n is the number ofelectrons generated at the electrode (4 in Equation 1), F is Faraday'sConstant (96,487 Coulomb/mol Vol O₂ at STP), A is the area of thecontact lens exposed to the gold cathode, and ΔP is the O₂ partialpressure difference across the lens at sea level pressure.

Apparent oxygen transmissibility (AOT) is obtained by multiplyingmeasured electric current (I) by the instrument cell constant “B” asshown in Equation 3. The term “apparent oxygen transmissibility” is usedsince diffusion resistance of the solution layer between the sample andelectrode (boundary layer) must be taken into account to obtain the trueoxygen transmissibility.Dk _(apparent) =BIt _(ave)  (3)The cell constant, B, is defined by the equation below.

$B = \frac{1}{{nFA}\Delta P}$The relationship between apparent oxygen transmissibility(Dk_(apparent)/t_(ave)) and true oxygen transmissibility (Dk/t_(ave)),is shown in Equation 4:

$\begin{matrix}{\frac{t_{ave}}{Dk_{apparent}} = {\frac{t_{ave}}{Dk} + \frac{t_{0}}{Dk_{0}}}} & (4)\end{matrix}$where t_(ave) is the average thickness of the material [in units of cm]over the area being measured and t₀/Dk₀ is the boundary layerresistance.

Herein, the reciprocal of apparent oxygen transmissibility was plottedversus lens thickness and oxygen permeability was obtained from theinverse slope of this plot. Herein, thickness of lens material wasvaried by stacking contact lenses (“Stack Method”). Additionalinformation concerning the stack method used herein to vary lensthickness is described in the literature (Fatt. ICLC 1984, 11, 175-187;Brennan et al. Clin Exp Optm. 1986, 37, 101-107; Weissman et al. CLAO J1991, 17, 62-64).

Oxygen transmissibility, Dk/t, is conveniently expressed in units ofbarrers/mm, where “t” is the average thickness of the material [in unitsof cm] over the area being measured and “barrer/mm” is defined as: (cm³oxygen)/(cm²)(sec)(mm Hg)ϕ×10⁻⁹.

Oxygen transmissibility (Dk/t) takes into account the thickness (t) ofthe contact lens and has the unit's mL O₂/(sec·cm² mm Hg). Oxygentransmissibility, Dk/t, is conveniently expressed in units ofbarrers/mm. These are the units commonly used in the art. Thus, in orderto be consistent with the use in the art, the unit “barrer” will havethe same meanings as defined above. For example, a lens having a Dk of120×10⁻¹¹ (mLO₂·cm)/(sec·cm²·mm Hg) means the same as a contact lenshaving a Dk of 120 barrers. A contact lens with oxygen permeability 120barrer and a thickness of 80 microns (0.8 mm, 0.08 cm) would have a Dk/tof 150×10⁻⁹ mL O₂/(sec·cm² mm Hg).

“High oxygen permeability,” as used herein in reference to a material ora contact lens, is characterized by an apparent oxygen permeability(Dk_(apparent)) of 40 barrers or more measured with a sample (film orlens) of 100 microns in thickness (e.g., 50 barrers or more, 60 barrersor more, 70 barrers or more, 80 barrers or more, 90 barrers or more, 100barrers or more, 110 barrers or more, 120 barrers or more, 130 barrersor more, 140 barrers or more, or 150 barrers or more).

The “ion permeability” through a lens correlates with both the IonofluxDiffusion Coefficient (D) and the Ionoton Ion Permeability Coefficient(P). The Ionoflux diffusion coefficient, D (mm²/min), is determined byFick's law of diffusion as follows:

$D = {- \frac{n^{\prime}}{\left( {A \times \frac{dc}{dx}} \right)}}$where n′ is the rate of ion transport (mol/min), A is the area of iontransport (mm²), dc is the concentration difference (mol/L), dx is thethickness of the lens (mm).

The Ionoton Ion Permeability Coefficient, P, is then determined inaccordance with the following equation:

${\ln\left( {1 - {2{C(t)}/{C(0)}}} \right)} = {- \frac{2{APt}}{Vd}}$where C(t) is the concentration of sodium ions at time tin the receivingcell, A is the membrane area (i.e., lens area exposed to cells), V isthe volume of the cell compartment, d is the average lens thickness.

ABBREVIATIONS

Abbreviation/ Acronym Name/Meaning PGLY or Gly Polyglycerol orpolyglycerol segment. Any of the possible isomers of polyglycerol arerepresented by PGLY or Gly. PGLY and Gly are used interchangeably hereinAC-PDMS-PGLY Polydimethylsiloxane block copolymers containingactinically cross-linkable polyglycerol side branches. UV-B locking AC-UV-Blocking Polydimethylsiloxane block PDMS-PGLY copolymers containingactinically cross-linkable polyglycerol side branches. BL-Blocking AC-Blue Light-Blocking Polydimethylsiloxane block PDMS-PGLY copolymerscontaining actinically cross-linkable polyglycerol side branches.CE-(PDMS- Chain extended block copolymers of PGLY)polydimethylsiloxane-polyglycerol UV-Blocking CE- UV-Blocking Chainextended block copolymers of (PDMS-PGLY)polydimethylsiloxane-polyglycerol BL-Blocking CE- Blue Light-BlockingChain extended block (PDMS-PGLY) copolymers ofpolydimethylsiloxane-polyglycerol AC-CE- Actinically curable chainextended block copolymers (PDMS-PGLY) ofpolydimethylsiloxane-polyglycerol UV-Blocking UV-Blocking Actinicallycurable chain extended AC-CE- block copolymers of polydimethylsiloxane-(PDMS-PGLY) polyglycerol BL-Blocking Blue Light-Blocking Actinicallycurable chain AC-CE- extended block (PDMS-PGLY) copolymers ofpolydimethylsiloxane-polyglycerol VAZO 522-2′-Azobis(2,4-dimethylvaleronitrile) VAZO 67 (AMBN)2,2′-Azodi(2-methylbutyronitrile) VAZO 88 (ACHN)(1,1′-Azobis(cyanocyclohexane) VAZO 56 WSP 4,4′-Azobis(4-cyanovalericAcid), 4,4′-Azobis(4- cyanopentanecarboxylic Acid) VAZO 68 WSP4,4′-(1,2-Diazenediyl)bis[4-cyanopentanoic Acid; >C=C< Generic symbolfor ethylenically unsaturated compound or group. Unsaturated monomersare those having carbon—carbon double bonds. Some examples ofunsaturated monomers include: 2-Hydroxyethyl methacrylate, glycerylmonomethacrylate, acrylic acid, acrylamide, dimethyl acrylamide,acryloyl chloride, and methyl methacrylate. GMMA Glycerylmonomethacrylate, 2,3-Dihydroxypropyl methacrylate, 2-Propionic acid,2-methyl-2,3- dihydroxypropyl ester HEMA 2-Hydroxyethyl methacrylate,1,2-Ethanediol mono(2-methylpropenoate), Glycol methacrylate, IPA2-propanol, isopropanol, isopropyl alcohol NVP 1-Vinyl-2-pyrrolidinone,N-Vinyl Pyrrolidone EGDMA Ethylene glycol di-methacrylate TGDMATetraethylene glycol dimethacrylate PEG or PEO Polyethylene glycol orpolyethylene oxide (PEO) SIGMA 3-Methacryloxy-2-Hydroxypropoxy(propylbis(trimethylsilyloxy)-methylsilane PDMS Polydimethylsiloxane TRIS3-methacryloxypropyl tris-(trimethylsiloxy) silane PDMS-MA Poly(dimethylsiloxane)-monomethacrylate MA-PDMS-MA Poly(dimethylsiloxane)-dimethacrylate PDMS-DA Polydimethylsiloxane-diacrylamideDGE-PDMS-DGE Poly(dimethyl siloxane), diglycidyl ether terminatedPDMS-DGE Poly(dimethyl siloxane), mono-glycidyl ether terminated BMEBenzoin methyl ether IRGACURE 184 1-hydroxy-cyclohexyl-phenyl-ketoneIRGACURE 500 1-hydroxy-cyclohexyl-phenyl-ketone (50 wt. %), benzophenone(50 wt. %) DARACURE Hydroxydimethylacetophenone 1173 (also known asIrgacure 1173) IRGACURE 29592-hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl- 1-propanone Irgacure 3692-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)- 1-butanone DAROCUR MBFMethylbenzoylformate IRGACURE 754 oxy-phenyl-acetic acid 2-[2 oxo-2phenyl-acetoxy- ethoxy]-ethyl ester and oxy-phenyl-acetic 2-[2-hydroxy-ethoxy]-ethyl ester IRGACURE 651 Alpha,alpha-dimethoxy-alpha-phenylacetophenone Irgacure 3692-Benzyl-2-(dimethylamino)-4-morpholino- butyrophenone IRGACURE 9072-Methyl-1-[4-(methylthio)phenyl]-2-(4- morpholinyl)-1-propanoneIRGACURE 1300 IRGACURE 369 (30 wt. %) + IRGACURE 651 (70 wt. %) DAROCURTPO Diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide DAROCUR 4265DAROCUR TPO (50 wt. %) + DARACURE 1173 (50 wt. %) DEAPDiethoxyacetophenone IRGACURE 651, Dimethoxyphenylacetophenone BDK,DMPA, IRGACURE 184 Benzoylcyclohexanol IRGACURE 819 Phosphine oxide,phenyl bis (2,4,6-trimethyl benzoyl) IRGACURE 2022 IRGACURE 819 (20 wt.%) + DARACURE 1173 (80 wt. %) IRGACURE 784 Bis (eta5-2,4-cyclopentadien-1-yl) Bis [2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium IRGACURE 250 Iodonium,(4-methylphenyl) [4-(2-methylpropyl) phenyl]-, hexafluoro-phosphate(1-)IRGACURE 379 2-(4-Methylbenzyl)-2-(dimethylamino)-4-morpholino-butyrophe-none IRGACURE 651,2,2-Dimethoxy-1,2-diphenylethan-1-one IEM 2-isocyanatoethylmethacrylateCQ Camphor Quinone DMBP 4-(Dimethylamino)benzophenone H-Nu Blue Cyanineborate Visible Light Photoinitiators 640, H-Nu available from SpectraGroup Limited Inc, 27800 660 Lemoyne Road, Suite J, Millbury, OH, 43447,USA H-Nu-IR 780, 815 Infrared Light Photoinitiators available fromSpectra Group Limited Inc, 27800 Lemoyne Road, Suite J, Millbury, OH,43447, USA MPPDASBD N-[3-(4-methylpyridino)propyl]-2-(p-N,N-diethylaminostyryl)benzothiazolium dibromide MPEA 2-methylprop-2-enoicanhydride, methacrylic anhydride MA Maleic Anhydride DMA Dimethylacrylamide DBTDL Dibutyltin dilaurate, [dibutyl(dodecanoyloxy) stannyl]dodecanoate DMAP N,N-Dimethylpyridin-4-amine; 4-Dimethylaminopyridine;N,N-Dimethylpyridin-4-amine TETOHA triethanolamine TEA Triethyl amineDiopter (D)^(a) Diopter (D) is a unit of measure of the refractive powerof a lens. One diopter is equal to the reciprocal of a focal length ofone meter. Dia^(a) or Diameter Dia is the contact lens diameter (chorddiameter). Contact lens diameter is the greatest distance across thecontact lens. Unless otherwise stated, contact lens diameter is reportedin units of millimeters (mm). BCR or BC BCR (base curve radius) or basecurve (BC) for a contact lens is the curvature of the back surface andis sometimes referred to as the back central optic radius (abbreviatedBCOR). Unless otherwise stated, contact lens base curve radius isreported in units of millimeter (mm). CT^(a) Axial or radial thicknessof a contact lens along the lens axis at the geometric center. Centerthickness of a contact lens. Power, Lens Power, lens power or Frontvertex power (F_(v) ^(a)): Power or F_(v) ^(a) Negative reciprocal ofthe front vertex focal length in meters of the optic zone in air,expressed in diopters. The front vertex focal length is the distancefrom the front vertex to the primary focal point of the optic zoneHydrogel^(a) A water absorbing (hydrophilic) material having anequilibrium water content greater than or equal to 10% in standardsaline at room temperature. Spherical A contact lens that brings aparaxial pencil of Contact Lens^(a) parallel rays to a single point offocus, and that has front and back optic zones consisting of spherical(non-toric) and non-aspheric) surfaces. Toric Lens^(a) A toric lens is acontact lens with either front or back optic zone having a toricsurface. Toric Surface^(a) A toric surface is described by a circlerotating about an off center line in its own plane. Meridians of leastand greatest curvature for these surfaces are perpendicular to eachother. Water Content^(a) Contact lens water content is the amount ofwater present in the lens expressed as a percentage of the total mass ofthe lens in its hydrated state under equilibrium conditions, whenimmersed in standard saline solution at a defined temperature. Contactlens water content may be measured gravimetrically, or by using arefractometer. ^(a)Description based on ANSI Z80.20-2010 (AmericanNational Standard) for Ophthalmic contact Lenses - Standard Terminology,Tolerances, Measurements and Physiochemical Properties.

Reference will now be made in detail to specific aspects of thedisclosed materials, compounds, compositions, articles, and methods,examples of which are illustrated in the accompanying examples andfigures.

Compositions

Described herein are compositions comprising an actinicallycross-linkable block copolymer of polydimethyl-siloxane (PDMS) with oneor more actinically curable polyglycerol branches. For example, theactinically cross-linkable block copolymers described herein compriseone or more actinically curable polyglycerol branches tethered to a PDMSmain chain.

Described herein are actinically-crosslinkable polysiloxane-polyglycerolblock copolymers comprising a polysiloxane prepolymer with one or moreactinically curable polyglycerol branches, wherein the actinicallycurable polyglycerol branches include crosslinking sites that can belocated near the junction of the polysiloxane prepolymer and thepolyglycerol branches or at any location along the polyglycerolbranches.

Described herein are compositions comprising anactinically-crosslinkable polysiloxane-polyglycerol block copolymerderived from: a polysiloxane prepolymer comprising a polyglycerol sidechain, the polyglycerol side chain comprising an ethylenicallyunsaturated group covalently linked thereto, wherein the ethylenicallyunsaturated group is actinically curable. The term “derived from” inreference to polymeric units in the polymer chain means that thepolymeric units are obtained from a specified monomer in apolymerization reaction. The polysiloxane prepolymer can comprise alinear or branched polysiloxane prepolymer, such that theactinically-crosslinkable polysiloxane-polyglycerol block copolymers cancomprise actinically-crosslinkable linear or branchedpolysiloxane-polyglycerol block copolymers. In some examples, thepolysiloxane prepolymer comprises polydimethyl siloxane (PDMS). Theethylenically unsaturated group can comprise any suitable actinicallycurable ethylenically unsaturated group. Exemplary ethylenicallyunsaturated groups include, but are not limited to, (meth)acryloyl,(meth)acrylamide, alkyl acrylamide, dialkyl acrylamide, allyl, vinyl,and styrenyl. In some examples, the ethylenically unsaturated group canbe directly linked to the polyglycerol branches of PDMS-PGLY. In someexamples, the ethylenically unsaturated group can be linked to thepolyglycerol side chain through a linking group (e.g., connector group).Examples of linking groups include, but are not limited to, thoseprovided in Table 1-Table 4. The * symbol is used in Table 1-Table 4 torepresent a radical that forms (theoretically) upon homolyticallyseparating linking groups from polyglycerol and cure groups.

TABLE 1 Bifunctional Monomers and linking groups.

Resulting Linking Group Note: If one were to homolytically cleave theReactants (Species) that react with liking group at the cure group andpolyglycerol polyglycerol OH units. junctions, the result is adi-radical species.

TABLE 2 Bifunctional Monomers and linking groups. Reaction of PDMS-PGLYwith Glycidylmethacrylate

Reactant One skilled in the art will recognized that reaction ofpolyglycerol units with certain Linking Groups reagents can lead to morethan one isomer. For Note: If one were to homolytically cleave example,reaction of polyglycerol with the liking group at the cure group andepoxide derivatives can lead to two different polyglycerol junctions,the result is a di- isomers as shown below. radical species.

TABLE 3 Bifunctional Monomers and linking groups.

Reactants Linking Group

TABLE 4 Bifunctional Monomers and linking groups. Linking Group Note: Ifone were to homolytically cleave the liking group at the cure group andpolyglycerol junctions, Reactants the result is a di-radical species.

Plus ortho and meta isomers

Plus ortho and meta isomers

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers can be defined by Formula I:

wherein

-   R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and J¹ are,    independently, alkyl, cycloalkyl, aryl, alkylpolyethylene oxide, or    polyglycerol, any of which is optionally substituted with halide,    hydroxy, thiol, carbonyl, alkoxy, alkylhydroxy, carboxyl, amino,    amido, alkyl, alkenyl, alkynyl, aryl, —NR^(x)R^(y),    —C(O)NR^(x)R^(y), azide, or a combination thereof;-   Q¹ and Q² are independently H, OH, amino, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl, any of which is    optionally substituted with epoxy, hydroxy, thiol, carbonyl, alkoxy,    alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,    —NR^(x)R^(y), —C(O)NR^(x)R^(y), azide, or a combination thereof;-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl;-   Cure Group comprises the ethylenically unsaturated group;-   a, c, d, e, f, g, h, i, j and k are, independently, an integer from    0 to 10,000,-   with the proviso that:-   at least one of e, g, h, and j is not 0, and-   at least one of d, f, i, and k is not 0; and-   b is an integer from 1 to 10,000.

Alkylpolyethylene oxide can comprise —(CH₂CH₂O)_(n)—OR¹², wherein n isan integer from 2 to 10,000 and R¹² is a substituted or unsubstitutedalkyl group (e.g., a C₁-C₁₈ alkyl group).

Polyglycerol can comprise —(C₃H₈O)_(n) wherein n is an integer from 2 to10,000. Polyglycerol can comprise linear or branched polyglycerol.Exemplary structures of linear and branched polyglycerol are depicted inFormula II, Formula III, Formula IV, Formula V, Formula VI, Formula VII,and Formula VIII. The molecular weight of branched polyglycerol can, forexample, be from 92 Daltons to 111,000 Daltons. Molecular weight ofpolyglycerol is determined by the number of repeat units and themolecular weight of the initiating species.

For example, the polyglycerol can comprise a linear polyglycerol definedby Formula II:

wherein

-   R¹³ is H, or an alkyl group or cycloalkyl group, either of which is    optionally substituted with halide, alkylthio, carbonyl, alkoxy,    carboxyl, amido, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,    aryl, —NR^(x)R^(y)R^(z), —C(O)NR^(x)R^(y), or a combination thereof;-   R^(x), R^(y), and R^(z) are independently H, OH, alkyl, alkenyl,    alkynyl, cycloalkyl, aryl, alkylaryl, or heteroaryl; and-   n is an integer from 2 to 1,000,000.

In some examples of Formula II, R¹³ comprises a nucleophilic groupcapable of initiating ring opening polymerization of glycidol. Examplesof such nucleophilic groups include, but are not limited to, OH,O-Alkyl, NR^(x)R^(y)R^(z), S—H, S-Alkyl, etc. In some examples, R¹³ cancomprise an amide substituent.

In some examples of Formula II, R¹³ can comprise CH₃(CH₂)_(m)O⁻Na⁺ wherem is an integer from 0 to 20; (CH₃)₃CO⁻Na⁺; NH₂; a linear, branched, orcyclic alkylamino group (e.g., CH₃(CH₂)_(m)NH where m is an integer from0 to 20, (CH₃)₂CHNH, piperidinyl, cyclopentyl-NH, cyclohexyl-NH); alinear, branched, or cyclic dialkylamine (e.g., (CH₃)₂N, CH₃(CH₃CH₂)N,(CH₃(CH₂)_(z))₂N where z is an integer from 1 to 20, piperidinyl); atrialkylammonium groups (e.g., (CH₃)₃N⁺, (CH₃CH₂)₃N⁺, (HOCH₂)₃N⁺,(HOCH₂CH₃)₃N⁺); a linear, branched, or cyclic alkylthiol (e.g.,CH₃(CH₂)_(m)S where m is an integer from 0 to 20, (CH₃)₂CHS, (CH₃)₃CS,cyclohexyl-S).

In some examples of Formula II, R¹³ can comprise X-Alkyl, where X═O,NH₂, S, NHR^(x), NR^(x)R^(y), NR^(x)R^(y)R^(z)±; alkyl groups includelinear, branched, or cyclic groups; and R^(x), R^(y), and R^(z) areindependently H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl,or heteroaryl. In some examples, of Formula II, R¹³ can comprise alinear, branched or cyclic structure such as —X—(CH₂)_(m)CH₃ where X═Oor S and m is from 0 to 20, e.g., —X-Propyl, X-butyl, —X-secbutyl,—X-Pentyl, —X-isopentyl, —X-cyclopentyl, —X-cyclohexyl,—X-methylcyclopentyl, —X-methylcyclohexyl. The alkyl groups canoptionally be substituted with various groups such as halide, alkoxy,thioether, carbonyl, carboxyl, amido, alkyl, cycloalkyl, alkenyl,cycloalkenyl, alkynyl, aryl, —C(O)NR^(x)R^(y), or a combination thereof.

In some examples of Formula II, R¹³ can comprise a linear, branched, orcyclic aminoalkyl structure, e.g., —NH(CH₂)_(m)CH₃ where m is from 0 to20. For example, R¹³ can comprise —NHAlkyl (e.g., —NHPropyl, —NHbutyl,—NHsecbutyl, —N-tbutyl, —NHPentyl, —NHisopentyl, —NHcyclopentyl,—NHcyclohexyl, —NHmethylcyclopently, —NH-methylcyclohexyl, etc.).

In some examples of Formula II, R¹³ can comprise a linear, branched, orcyclic amino dialkyl structure, e.g., —N[(CH₂)_(m)CH₃)]₂ where m is from0 to 20. For example, R¹³ can comprise —N(Alkyl)₂ (e.g., —N(propyl)₂,—N(butyl)₂, —N(secbutyl)₂, —N-(t-butyl)₂, —N(pentyl)₂, —N(isopentyl)₂,—N(cyclopentyl)₂, —N(cyclohexyl)₂, —N(methylcyclopentyl)₂,—N(methylcyclohexyl)₂, etc.).

In some examples of Formula II, R¹³ can comprise a linear, branched, orcyclic amino trialkyl structure, e.g. —N[(CH₂)_(m)CH₃)]₃ where m is from0 to 20. For example, R¹³ can comprise —N(Alkyl)₃, (e.g., —N(propyl)₃,—N(butyl)₃, —N(secbutyl)₃, —N(t-butyl)₃, —N(pentyl)₃, —N(isopentyl)₃,—N(cyclopentyl)₃, —N(cyclohexyl)₃, —N(methylcyclopentyl)₃,—N(methylcyclohexyl)₃, 1-Methylpiperidinyl, etc.).

In some examples of Formula II, R¹³ can comprise4-[1-(Aminomethyl)cyclopentanecarbonyl]-1-methylpiperazin-2-one,2-Aminobutanamide, 3-Aminobutanamide, 4-Aminobutyramide,5-aminopentanamide, N-(2-Aminoethyl)-acetamide,2-Amino-N-methyl-acetamide, N-(2-Hydroxyethyl)-acetamide,N-(2-Hydroxyethyl)-formamide, N-(2-Hydroxyethyl)-propanamide, orN-(2-Mercaptoethyl)-acetamide.

In some examples, the polyglycerol comprises a branched polyglyceroldefined by Formula III:

wherein

-   R¹⁴ is H, alkyl, or cycloalkyl, either of which is optionally    substituted with halide, hydroxy, carbonyl, alkoxy, alkylhydroxy,    carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl, thioether,    —NR^(x)R^(y), —C(O)NR^(x)R^(y), or a combination thereof;-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl; and-   n is an integer from 1 to 10,000.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula IV:

wherein n is an integer from 1 to 10,000.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula V:

wherein

-   R¹⁵ and R¹⁶ are, independently, H, alkyl, or cycloalkyl, either of    which is optionally substituted with halide, hydroxy, thioether,    carbonyl, alkoxy, alkylhydroxy, carboxyl, amino, amido, alkyl,    alkenyl, alkynyl, aryl, —NR^(x)R^(y), —C(O)NR^(x)R^(y), or a    combination thereof; or-   R¹⁵ and R¹⁶, together with the atoms to which they are attached,    form a 3-10 membered cyclic moiety, wherein any of the additional    atoms are optionally heteroatoms and the 3-10 membered cyclic moiety    is optionally substituted with halide, hydroxy, thiol, carbonyl,    alkoxy, alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl,    alkynyl, aryl, —NR^(x)R^(y), —C(O)NR^(x)R^(y), or a combination    thereof;-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl; and-   n is an integer from 1 to 10,000.

In some examples of Formula V, R¹⁵ and R¹⁶ are, independently, H,CH₃(CH₂)_(m) where m is an integer from 1 to 20, cyclopentyl, orcyclohexyl. In some examples of Formula V, R¹⁵ and R¹⁶, together withwhich the atoms to which they are attached, comprise a piperidinylgroup.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula VI:

wherein n is an integer from 1 to 10,000.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula VII:

wherein

-   R¹⁷, R¹⁸, and R¹⁹ are, independently, H, alkyl, or cycloalkyl,    either of which is optionally substituted with halide, hydroxy,    thioalkyl, carbonyl, alkoxy, alkylhydroxy, carboxyl, amino, amido,    alkyl, alkenyl, alkynyl, aryl, —NR^(x)R^(y), —C(O)NR^(x)R^(y), or a    combination thereof; or-   two or more of R¹⁷, R¹⁸, and R¹⁹, together with the atoms to which    they are attached, form a 3-10 membered cyclic moiety, wherein any    of the additional atoms are optionally heteroatoms and the 3-10    membered cyclic moiety is optionally substituted with halide,    hydroxy, thioether, carbonyl, alkoxy, alkylhydroxy, carboxyl, amino,    amido, alkyl, alkenyl, alkynyl, aryl, —NR^(x)R^(y),    —C(O)NR^(x)R^(y), or a combination thereof;-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl; and-   n is an integer from 1 to 10,000.

In some examples of Formula VII, R¹⁷, R¹⁸, and R¹⁹ are, independently,H, CH₃(CH₂)_(m) where m is an integer from 0 to 20, cyclopentyl,cyclohexyl, CH₂OH, or OHCH₂CH₃. In some examples of Formula VII, two ofR¹⁷, R¹⁸, and R¹⁹, together with which the atoms to which they areattached, comprise a piperidinyl group.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula VIII:

wherein

-   R²⁰ is H, alkyl, or cycloalkyl, any of which is optionally    substituted with halide, hydroxy, thioether, carbonyl, alkoxy,    alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,    —NR^(x)R^(y), —C(O)NR^(x)R^(y), or a combination thereof;-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl; and-   n is an integer from 1 to 10,000.

In some examples of Formula VIII, R²⁰ is C₁-C₁₂, alkyl, C₃-C₁₂cycloalkyl, C₁-C₂₀ alkoxy, or C₃-C₂₀ cycloalkoxy, any of which isoptionally substituted. In some examples of Formula VIII, R²⁰ isunsubstituted C₁-C₁₂ alkyl, unsubstituted C₃-C₁₂ cycloalkyl,unsubstituted C₁-C₂₀ alkoxy, or unsubstituted C₃-C₂₀ cycloalkoxy. Insome examples of Formula VIII, R²⁰ is CH₃(CH₂)_(m) where m is an integerfrom 0 to 20.

The polyglycerol and/or polyglycerol side chains present in theactinically-crosslinkable polysiloxane-polyglycerol block copolymers canbe located at the termini of the polysiloxane prepolymer chains or atany location in between the termini. Furthermore, the length of thepolysiloxane prepolymer and polyglycerol chains may vary.

In some examples of Formula I

R¹-R¹¹ and J¹ are, independently, C₁-C₁₈ alkyl, C₃-C₁₈ cycloalkyl,C₃-C₂₀ aryl, alkylpolyethylene oxide, or polyglycerol, any of which isoptionally substituted with halide, hydroxy, thiol, carbonyl, alkoxy,alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,—NR^(x)R^(y), —C(O)NR^(x)R^(y), azide, or a combination thereof.

In some examples of Formula I, R¹-R¹¹ and J¹ are, independently, linearC₁-C₁₈ alkyl, branched C₂-C₁₈ alkyl, cyclic C₃-C₁₈ alkyl, C₃-C₂₀ aryl,linear C₁-C₁₈ perfluoroalkyl, branched C₂-C₁₈ perfluoroalkyl, cyclicC₃-C₁₈ perfluoroalkyl, alkyl-polyethylene oxide, linear polyglycerol, orbranched polyglycerol, any of which is optionally substituted.

In some examples of Formula I, R¹-R¹¹ and J¹ are, independently, linearC₁-C₁₈ alkyl, branched C₂-C₁₈ alkyl, cyclic C₃-C₁₈ alkyl, C₃-C₂₀ aryl,linear C₁-C₁₈ perfluoroalkyl, branched C₂-C₁₈ perfluoroalkyl, cyclicC₃-C₁₈ perfluoroalkyl, alkyl-polyethylene oxide, a linear polyglycerolof Formula III, or a branched polyglycerol of any of Formula IV-FormulaVIII, any of which is optionally substituted.

In some examples of Formula I, R¹-R¹⁰ are, independently, linear C₁-C₁₈alkyl, any of which is optionally substituted. In some examples ofFormula I, R¹-R¹⁰ are, independently, unsubstituted linear C₁-C₁₈ alkyl.In some examples of Formula I, R¹-R¹⁰ are, independently, linear C₁-C₁₂,alkyl, any of which is optionally substituted. In some examples ofFormula I, R¹-R¹⁰ are, independently, unsubstituted linear C₁-C₁₂,alkyl. In some examples of Formula I, R¹-R¹⁰ are, independently, linearC₁-C₈ alkyl, any of which is optionally substituted. In some examples ofFormula I, R¹-R¹⁰ are, independently, unsubstituted linear C₁-C₈ alkyl.In some examples of Formula I, R¹-R¹⁰ are, independently, linear C₁-C₄alkyl, any of which is optionally substituted. In some examples ofFormula I, R¹-R¹⁰ are, independently, unsubstituted linear C₁-C₄ alkyl.In some examples of Formula I, R¹-R¹⁰ are the same. In some examples ofFormula I, R¹-R¹⁰ are all methyl. In some examples, the polysiloxaneprepolymer comprises polydimethyl siloxane.

In some examples of Formula I, J¹ is C₁-C₁₈ alkoxy which is optionallysubstituted. In some examples of Formula I, J¹ is unsubstituted C₁-C₁₈alkoxy. In some examples of Formula I, J¹ is C₁-C₁₂, alkoxy which isoptionally substituted. In some examples of Formula I, J¹ isunsubstituted alkoxy. In some examples of Formula I, J¹ is C₁-C₈ alkoxywhich is optionally substituted. In some examples of Formula I, J¹ isunsubstituted C₁-C₈ alkoxy. In some examples of Formula I, J¹ is C₁-C₄alkoxy which is optionally substituted. In some examples of Formula I,J¹ is unsubstituted C₁-C₄ alkoxy. In some examples of Formula I, J¹ isOCH₂.

In some examples of Formula I, Q¹ and Q² are independently H, OH, aryl,epoxide, alkanol, alkylthio, alkenylthio, arylthio, amine, alkylamine,dialkylamine, (meth)acrylate, (meth)acrylamide, dialkyl(meth)acrylamide, vinyl, ketone, aldehyde, carboxylic acid, anhydride,or azide, any of which is optionally substituted.

In some examples of Formula I, Q¹ and Q² are independently C₁-C₁₈ alkyl,C₃-C₂₀ aryl, C₁-C₁₈ perfluoroalkyl, C₁-C₁₈ alkanol (e.g., C_(n)H_(2n)OH,such as CH₂OH, CH₂CH₂—OH, CH₂CH₂CH₂OH, CH₂CH₂CH₂CH₂OH, (CH₃)₂COH,CH₂CH₂OHCH₂CH₃, (CH₃)₃CCHOH, CH₂CHOHCH₂CH(CH₃)₂, CH₂CH₂CHOHCH(CH₃)₂,CH₂CH₂CH₂COH(CH₃)₂, CH₂CH₂CH₂CHCH₃CH₂OH), C₁-C₁₈ alkylthiol (e.g.,C_(n)H_(2n)SH, such as CH₂SH, CH₂CH₂SH, CH₂CH₂CH₂SH, CH₂CH₂CH₂CH₂SH),C₁-C₁₈ alkylamine (e.g., a primary alkyl amine C_(n)H_(2n+1)NH₂), C₁-C₁₈dialkylamine (e.g., a secondary amine C_(n)H_(2n+1)NHR′, where R′ ismethyl, ethyl, propyl, isopropyl, butyl, sec butyl, t-butyl, pentyl,cyclopentyl, cyclohexyl, heptyl, etc.), or an ethylenically unsaturatedgroup (e.g., acrylate, methacrylate, acrylamide, methacrylamide, allyl,and styryl), any of which is optionally substituted (e.g., with an epoxygroup).

In some examples of Formula I, the Cure Group can be selected from thegroup consisting of:

wherein

-   R^(a) is H, alkyl, or cycloalkyl, either of which is optionally    substituted with halide, hydroxy, alkylthiol, carbonyl, alkoxy,    alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,    —NR^(x)R^(y), —C(O)NR^(x)R^(y), or a combination thereof; and-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl.

In some examples of Formula I, the cure group is

In some examples of Formula I, the cure group is

In some examples of Formula I, the cure group is

wherein R^(a) is C₁-C₁₈ alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₁₈ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is C₁-C₁₂ alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₁₂ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is C₁-C₈ alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₈ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is C₁-C₄ alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₄ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is methyl.

In some examples of Formula I, the cure group is

In some examples of Formula I, the cure group is

wherein R^(a) is C₁-C₁₈ alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₁₈ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is C₁-C₁₂, alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₁₂ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is C₁-C₈ alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₈ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is C₁-C₄ alkyl which is optionally substituted. In someexamples of Formula I, the cure group is

wherein R^(a) is unsubstituted C₁-C₄ alkyl. In some examples of FormulaI, the cure group is

wherein R^(a) is methyl.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer is defined by Formula IX:

whereina, c, e, f, i, j and k are, independently, an integer from 0 to 10,000;with the proviso that:

at least one of e and j is not 0, and

at least one of f, i, and k is not 0; and

b is an integer from 1 to 10,000.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer is defined by Formula X:

whereina, c, e, f, i, j and k are, independently, an integer from 0 to 10,000;with the proviso that:

at least one of e and j is not 0, and

at least one of f, i, and k is not 0; and

b is an integer from 1 to 10,000.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer is defined by Formula XI:

whereina, c, e, f, i, j and k are, independently, an integer from 0 to 10,000;with the proviso that:

at least one of e and j is not 0, and

at least one of f, i, and k is not 0; and

b is an integer from 1 to 10,000.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers are further derived from oneor more monomer units selected from the group consisting ofN-vinyl-2-pyrrolidone (NVP), N,N-dimethyl acrylamide (DMA),dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, vinylacetate, 2-Hydroxyethyl methacrylate (HEMA), glycerol mono-methacrylate(GMMA), N-Hydroxyethyl acrylamide (NHA),N-(2,3-Dihydroxypropyl)acrylamide (NDHA), N-(hydroxyl methyl)acrylamidesolution (NHMA), N-[3-(Dimethylamino)propyl]methacrylamide, aC₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight averagemolecular weight of from 300 to 2000, N-vinyl-N-methyl isopropyl amide,N-vinyl-N-methyl acetamide, and mixtures thereof.

The actinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein comprise two or more polymeric chains (blocks), whichare structurally different and chemically bonded to each other. Undercertain conditions, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers can segregate into a varietyof ordered structures.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers can be subjected to chemicalreactions such as cross-linking of actinically curable groups,substitution reactions, and addition reactions, “click” chemicalreactions, polymerization reactions, or any number of chemical reactionsknown in the art to form ordered block copolymer structures that aresubstantially locked in place. In some examples, theactinically-crosslinkable polysiloxane-polyglycerol block copolymers canundergo cross-linking reactions.

Also disclosed herein are chain extended actinically-crosslinkablepolysiloxane-polyglycerol block copolymers. Chain extendedactinically-crosslinkable polysiloxane-polyglycerol block copolymers(CE-AC-(PDMS-PGLY) can be prepared through reaction of apolysiloxane-polyglycerol block copolymer with a difunctional reagent(e.g., diisocyanate, diepoxide, etc.) through a chain extension process,such as described herein below. Cure groups can be added to thepolysiloxane-polyglycerol unit before or after chain extension. In someexamples, it can be preferable to add cure groups after chain extensionprocess, e.g., when the cure group(s) are heat sensitive.

In some examples, the chain extended actinically-crosslinkablepolysiloxane-polyglycerol block copolymers can be defined by FormulaXII:

wherein

-   R¹, R^(1′), R², R^(2′), R³, R^(3′), R⁴, R^(4′), R⁵, R^(5′), R⁶,    R^(6′), R⁷, R^(7′), R⁸, R^(8′), R⁹, R^(9′), R¹⁰, R^(10′), R¹¹,    R^(11′), J¹, and J^(1′) are, independently, alkyl, cycloalkyl, aryl,    alkylpolyethylene oxide, or polyglycerol, any of which is optionally    substituted with halide, hydroxy, thiol, carbonyl, alkoxy,    alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,    —NR^(x)R^(y), —C(O)NR^(x)R^(y), azide, or a combination thereof;-   Q¹, Q^(1′), Q², and Q^(2′) are independently H, OH, amino, alkyl,    alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, or heteroaryl, any of    which is optionally substituted with epoxy, hydroxy, thiol,    carbonyl, alkoxy, alkylhydroxy, carboxyl, amino, amido, alkyl,    alkenyl, alkynyl, aryl, —NR^(x)R^(y), —C(O)NR^(x)R^(y), azide, or a    combination thereof;-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl;-   Cure Group and Cure Group′ independently comprise an ethylenically    unsaturated group;-   Z is a chain extension group;-   a, a′, c, c′, d, d′, e, e′, f, f′, g, g′, h, h′, j, j′, k, and k′    are, independently, an integer from 0 to 10,000,-   with the proviso that:-   at least one of e, g, h, and j is not 0,-   at least one of e′, g′, h′, and j′ is not 0,-   at least one of d, f, i, and k is not 0, and-   at least one of d′, f′, i′, and k′ is not 0; and-   b and b′ are independently an integer from 1 to 10,000.

In some examples of Formula XII, the chain extension group can comprisea linking group such as those described in Table 1-Table 4.

In some examples of Formula XII, R¹-R¹¹, R^(1′)-R^(11′), J¹, and J^(1′)are, independently, C₁-C₁₈ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₂₀ aryl,alkylpolyethylene oxide, or polyglycerol, any of which is optionallysubstituted with halide, hydroxy, thiol, carbonyl, alkoxy, alkylhydroxy,carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl, —NR^(x)R^(y),—C(O)NR^(x)R^(y), azide, or a combination thereof.

In some examples of Formula XII, R¹-R¹¹, R^(1′)-R^(11′), J¹, and J^(1′)are, independently, linear C₁-C₁₈ alkyl, branched C₂-C₁₈ alkyl, cyclicC₃-C₁₈ alkyl, C₃-C₂₀ aryl, linear C₁-C₁₈ perfluoroalkyl, branched C₂-C₁₈perfluoroalkyl, cyclic C₃-C₁₈ perfluoroalkyl, alkyl-polyethylene oxide,linear polyglycerol, or branched polyglycerol, any of which isoptionally substituted.

In some examples of Formula XII, R¹-R¹¹, R^(1′)-R^(11′), J¹, and J^(1′)are, independently, linear C₁-C₁₈ alkyl, branched C₂-C₁₈ alkyl, cyclicC₃-C₁₈ alkyl, C₃-C₂₀ aryl, linear C₁-C₁₈ perfluoroalkyl, branched C₂-C₁₈perfluoroalkyl, cyclic C₃-C₁₈ perfluoroalkyl, alkyl-polyethylene oxide,a linear polyglycerol of Formula III, or a branched polyglycerol of anyof Formula IV-Formula VIII, any of which is optionally substituted.

In some examples of Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′) are,independently, linear C₁-C₁₈ alkyl, any of which is optionallysubstituted. In some examples of Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′)are, independently, unsubstituted linear C₁-C₁₈ alkyl. In some examplesof Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′) are, independently, linearC₁-C₁₂ alkyl, any of which is optionally substituted. In some examplesof Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′) are, independently,unsubstituted linear C₁-C₁₂ alkyl. In some examples of Formula XII,R¹-R¹⁰ and R^(1′)-R^(10′) are, independently, linear C₁-C₈ alkyl, any ofwhich is optionally substituted. In some examples of Formula XII, R¹-R¹⁰and R^(1′)-R^(10′) are, independently, unsubstituted linear C₁-C₈ alkyl.In some examples of Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′) are,independently, linear C₁-C₄ alkyl, any of which is optionallysubstituted. In some examples of Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′)are, independently, unsubstituted linear C₁-C₄ alkyl. In some examplesof Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′) are the same. In some examplesof Formula XII, R¹-R¹⁰ and R^(1′)-R^(10′) are all methyl. In someexamples, the polysiloxane prepolymer comprises polydimethyl siloxane.

In some examples of Formula XII, J¹ and J^(1′) are independently C₁-C₁₈alkoxy which is optionally substituted. In some examples of Formula XII,J¹ and J^(1′) are independently unsubstituted C₁-C₁₈ alkoxy. In someexamples of Formula XII, J¹ and J^(1′) are independently C₁-C₁₂ alkoxywhich is optionally substituted. In some examples of Formula XII, J¹ andJ^(1′) are independently unsubstituted alkoxy. In some examples ofFormula XII, J¹ and J^(1′) are independently C₁-C₈ alkoxy which isoptionally substituted. In some examples of Formula XII, J¹ and J^(1′)are independently unsubstituted C₁-C₈ alkoxy. In some examples ofFormula XII, J¹ and J^(1′) are independently C₁-C₄ alkoxy which isoptionally substituted. In some examples of Formula XII, J¹ and J^(1′)are independently unsubstituted C₁-C₄ alkoxy. In some examples ofFormula XII, J¹ and J^(1′) are OCH₂.

In some examples of Formula XII, Q¹, Q^(1′), Q², and Q^(2′) areindependently H, OH, aryl, epoxide, alkanol, alkylthio, alkenylthio,arylthio, amine, alkylamine, dialkylamine, (meth)acrylate,(meth)acrylamide, dialkyl (meth)acrylamide, vinyl, ketone, aldehyde,carboxylic acid, anhydride, or azide, any of which is optionallysubstituted.

In some examples of Formula XII, Q¹, Q^(1′), Q², and Q^(2′) areindependently C₁-C₁₈ alkyl, C₃-C₂₀ aryl, C₁-C₁₈ perfluoroalkyl, C₁-C₁₈alkanol (e.g., C_(n)H_(2n)OH, such as CH₂OH, CH₂CH₂—OH, CH₂CH₂CH₂OH,CH₂CH₂CH₂CH₂OH, (CH₃)₂COH, CH₂CH₂OHCH₂CH₃, (CH₃)₃CCHOH,CH₂CHOHCH₂CH(CH₃)₂, CH₂CH₂CHOHCH(CH₃)₂, CH₂CH₂CH₂COH(CH₃)₂,CH₂CH₂CH₂CHCH₃CH₂OH), C₁-C₁₈ alkylthiol (e.g., C_(n)H_(2n)SH, such asCH₂SH, CH₂CH₂SH, CH₂CH₂CH₂SH, CH₂CH₂CH₂CH₂SH), C₁-C₁₈ alkylamine (e.g.,a primary alkyl amine C_(n)H_(2n+1)NH₂), C₁-C₁₈ dialkylamine (e.g., asecondary amine C_(n)H_(2n+1)NHR′, where R′ is methyl, ethyl, propyl,isopropyl, butyl, sec butyl, t-butyl, pentyl, cyclopentyl, cyclohexyl,heptyl, etc.), or an ethylenically unsaturated group (e.g., acrylate,methacrylate, acrylamide, methacrylamide, allyl, and styryl), any ofwhich is optionally substituted (e.g., with an epoxy group).

In some examples of Formula XII, Cure Group and cure Group′ canindependently be selected from the group consisting of:

wherein

-   R^(a) is H, alkyl, or cycloalkyl, either of which is optionally    substituted with halide, hydroxy, alkylthiol, carbonyl, alkoxy,    alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,    —NR^(x)R^(y), —C(O)NR^(x)R^(y), or a combination thereof; and-   R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,    cycloalkyl, aryl, alkylaryl, or heteroaryl.

In some examples of Formula XII, Cure Group and Cure Group′ are

In some examples of Formula XII, Cure Group and Cure Group′ areindependently

In some examples of Formula XII, Cure Group and Cure Group′ areindependently

wherein R^(a) is C₁-C₁₈ alkyl which is optionally substituted. In someexamples of Formula XII, Cure Group and Cure Group′ are independently

wherein R^(a) is unsubstituted C₁-C₁₈ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are independently

wherein R^(a) is C₁-C₁₂ alkyl which is optionally substituted. In someexamples of Formula XII, Cure Group and Cure Group′ are independently

wherein R^(a) is unsubstituted C₁-C₁₂ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are independently

wherein R^(a) is C₁-C₈ alkyl which is optionally substituted.

In some examples of Formula XII, Cure Group and Cure Group′ areindependently

wherein R^(a) is unsubstituted C₁-C₈ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are independently

wherein R^(a) is C₁-C₄ alkyl which is optionally substituted. In someexamples of Formula XII, Cure Group and Cure Group′ are independently

wherein R^(a) is unsubstituted C₁-C₄ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are

wherein R^(a) is methyl.

In some examples of Formula XII, Cure Group and Cure Group′ areindependently

In some examples of Formula XII, Cure Group and Cure Group′ areindependently

wherein R^(a) is C₁-C₁₈ alkyl which is optionally substituted. In someexamples of Formula XII, Cure Group and Cure Group′ are independently

wherein R^(a) is unsubstituted C₁-C₁₈ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are independently

wherein

R^(a) is C₁-C₁₂ alkyl which is optionally substituted. In some examplesof Formula XII, Cure Group and Cure Group′ are independently

wherein R^(a) is unsubstituted C₁-C₁₂ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are independently

wherein R^(a) is C₁-C₈ alkyl which is optionally substituted. In someexamples of Formula XII, Cure Group and Cure Group′ are independently

wherein R^(a) is unsubstituted C₁-C₈ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are independently

wherein R^(a) is C₁-C₄ alkyl which is optionally substituted. In someexamples of Formula XII, Cure Group and Cure Group′ are independently

wherein R^(a) is unsubstituted C₁-C₄ alkyl. In some examples of FormulaXII, Cure Group and Cure Group′ are

wherein R^(a) is methyl.

Also disclosed herein are silicone hydrogel compositions comprising theactinically-crosslinkable polysiloxane-polyglycerol block copolymerscrosslinked with a crosslinker. Cross-linkers include, for example,vinylic cross-linkers, difunctional isocyanate cross-linkers,difunctional epoxide cross-linkers, difunctional alkyl halides (e.g.,difunctional acid halides), difunctional-anhydrides, bis-halo-alkylderivatives, activated esters, or any number of difunctional reagentscapable for forming chemical bonds with polyglycerol OH groups.

Examples of vinylic cross-linkers include but are not limited to:Ethylene glycol dimethacrylate; Triethylene glycol dimethacrylate;Diethyleneglycol Dimethacrylate; 1,3-Glycerol Dimethacrylate;1,6-Hexanediol Dimethacrylate; 1,12-Dodecanediol Dimethacrylate;Trimethylolpropane Trimethacrylate; Poly (Ethyleneglycol) (400)Dimethacrylate; Isophorone Urethane Dimethacrylate;N,N′-Methylenebisacrylamide; 1,6-Hexamethylene bis-Methacrylamide;N,N′-Hexamethylenebismethacrylamide; N,N′-iso-Valerylidenebis-Methacrylamide;N,N′-Nonamethylenebisacrylamidem-Xylenebisacrylamide; 1,10-DecamethyleneGlycol Diacrylate; 1,2-Propanediol Diacrylate; 1,3-ButanediolDiacrylate; 1,3-Propanediol Diacrylate; 1,4-CyclohexanedimethylDiacrylate; 1,5-Pentanediol Diacrylate; 1,9-Nonanediol Diacrylate;2,2,3,3,4,4,5,5-Octafluoro-1,6-Hexanediol Diacrylate;2,2,3,3-Tetrafluoro-1,4-Butanediol Diacrylate; 2-Butene-1,4-Diacrylate;Aliphatic Urethane Acrylate in Tripropylene Glycol Diacrylate;Diethylene Glycol Diacrylate; Ethylene Diacrylate; neo-Pentyl GlycolDiacrylate; Sorbitol Diacrylate; Hexamethylene Diacrylate; ThiolDiethylene Glycol Diacrylate; Tetraethylene Glycol Diacrylate;Triethylene Glycol Diacrylate; Bisphenol A Glycidyl Methacrylate;Pentaerythritol Tetramethacrylate; 1,3-Divinyltetramethyl-disiloxane;3-Methacryloxypropyl Tris-(Vinyldimethylsiloxy) Silane;1,1,5,5-Tetrahydroperfluoro-1,5-Pentanediol Dimethacrylate;2,2,3,3,4,4,5,5-Octafluoro-1,6-Hexanediol Diacrylate;2,2,3,3,4,4,5,5-Octafluoro-1,6-Hexanediol Dimethacrylate;divinylbenzene; diallylbutyl ether; and diallylbisphenol-A.

Examples of difunctional isocyanate cross-linkers include but are notlimited to: Isophorone diisocyanate (IPDI), hexamethylene diisocyanate(HDI), methylene dicyclohexyl diisocyanate, toluene diisocyanate (TDI),Tolylene-2,4-diisocyanate, Tolylene-2,6-diisocyanate,trans-1,4-Cyclohexylene diisocyanate, Poly(propylene glycol), tolylene2,4-diisocyanate terminated, 1,4-Diisocyanatobutane,1,8-Diisocyanatooctane, 1,3-Bis(1-isocyanato-1-methylethyl)benzene,2,2,4-Trimethylhexamethylene Diisocyanate, 2,4,4-TrimethylhexamethyleneDiisocyanate, 1,4-Phenylene diisocyanate, 1,3-Phenylene diisocyanate,m-Xylylene diisocyanate, and methylenediphenyl diisocyanate (MDI).Depending on the ratio of diisocyanate to PDMS-PGLY, chain extension orcrosslinking can occur.

Examples of difunctional epoxide cross-linkers include but are notlimited to: diglycidyl ether, Bisphenol A diglycidyl ether, Glyceroldiglycidyl ether, resorcinol diglycidyl ether, diglycidyl ether,bis(3,4-epoxycyclohexylmethyl) adipate, poly(ethylene glycol) diglycidylether, Bis[4-(glycidyloxy)phenyl]methane, 1,3-Butadiene diepoxide,1,4-Butanediol diglycidyl ether, 1,4-Butanediol diglycidyl ether,1,3-Butanediol diglycidyl ether, Bisphenol F diglycidyl ether, BisphenolA propoxylate diglycidyl ether, neopentyl glycol diglycidyl ether,N,N-Diglycidyl-4-glycidyloxyaniline, 4,4′-Isopropylidenediphenoldiglycidyl ether, Poly(propylene glycol) diglycidyl ether,Dicyclopentadiene dioxide, 1,2,5,6-Diepoxycyclooctane,1,2,7,8-Diepoxyoctane, Diglycidyl 1,2-cyclohexanedicarboxylate,3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate,2,5-bis[(2-oxiranylmethoxy)-methyl]-furan (BOF) and2,5-bis[(2-oxiranylmethoxy)methyl]-benzene, Poly(dimethyl siloxane),tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM),tri-glycidyl-aminophenol, e.3-(3-glycidoxypropyl)-1,1,1,3,5,5,5-heptamethyltrisiloxsane,1-epoxyethyl-3,4-epoxycyclohexane, 1,3,5-Triglycidyl isocyanurate,PC-1000 Epoxy Siloxane Monomer (available from Polyset), PC-1035 EpoxySiloxane Monomer (available from Polyset), Poly(dimethylsiloxane),diglycidyl ether terminated (average Mn ˜800, available from SIGMAALDRICH), epoxy terminated Poly(dimethylsiloxanes) available from ShinEtsu Silicone Company and sold under the trade names KF-105; X-22-163A;X-22-163B; X-22-163C; X-22-169AS; X-22-169B available from Shin EtsuSilicone Company; bis[2-(3,4-epoxycyclohexyl)-ethyltetramethyldisiloxane, and 2,4,6,8-Tetramethyl-2,4,6,8-tetrakis(propylglycidyl ether)cyclotetrasiloxane. Depending on the ratio of diepoxideto PDMS-PGLY, chain extension or crosslinking can occur.

Examples of difunctional alkyl halides include but are not limited to:1,4-Dibromobutane, 1,5-Dibromopentane, 1,6-Dibromohexane,1,8-Dibromooctane. Depending on the ratio of diepoxide to PDMS-PGLY,chain extension or crosslinking can occur.

Examples of difunctional acid chlorides include but are not limited to:malonyl chloride, isophthaloyl di-acid chloride, sebacoyl chloride,dodecanedioyl dichloride, octanedioic acid dichloride, fumaryl chloride,glutaryl chloride. Depending on the ratio of diacid chloride toPDMS-PGLY, chain extension or crosslinking can occur.

Examples of difunctional-anhydrides include but are not limited to:Diethylene-triaminepentaacetic dianhydride,4,4′-(4,4′-Isopropylidenediphenoxy) bis(phthalic anhydride),4,4′-(Hexafluoroisopropylidene)-diphthalic anhydride, bis(phthalicanhydride), 4,4′-Oxydiphthalic anhydride,3,3′,4,4′-Biphenyltetracarboxylic dianhydride,Benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, and Pyromelliticdi-anhydride. Silicones containing two or more anhydride groups perpolymer chain many also be used as cross-linkers. The dual end anhydrideterminated Poly(dimethylsiloxanes) available from Shin Etsu SiliconeCompany and sold under the trade name X-22-2290AS may also be used as across-linking agent. Depending on the ratio of dianhydride to PDMS-PGLY,chain extension or crosslinking can occur.

Examples of Bis-haloalkylether-derivatives include: Bis(chloromethyl)ether, Bis(bromomethyl) ether, bis(iodomethyl) ether, bis(chloroethyl)ether, bis(bromoethyl) ether, bis(iodoethyl) ether.

Activated Esters such as: 3,3′-Dithiodipropionic aciddi(N-hydroxysuccinimide ester) may also be used.

Dual end reactive silicones may also be used as cross-linking agents orchain extenders. Examples reactive silicones bearing dual endmethacrylate functionality sold under the trade names X-22-164A;X-22-164B area available from Shin Etsu Silicone Company.

In some examples, the silicone hydrogel compositions further comprise ahydrophilic monomer, a hydrophobic monomer, an amphiphilic monomer, azwitterionic monomer, an antimicrobial monomer, a UV-blocker, a bluelight blocker, a dye, a pigment, a solvent, or a combination thereof.

Suitable hydrophilic monomers comprise, for example,hydroxyl-substituted lower alkyl (C₁ to C₈) (meth)acrylates,(meth)acrylamide, (lower allyl) (meth)acrylamides, ethoxylated(meth)acrylates, hydroxyl-substituted (lower alkyl)(meth)acrylamides,hydroxyl-substituted lower alkyl vinyl ethers, sodium vinyl sulfonate,sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid,methyl vinyl ether, vinyl acetate, and methacrylated glyco-monomers.Examples of hydrophilic monomers include but are not limited toN-Hydroxyethyl acrylamide; N,N-dimethyl acrylamide (DMA); N-Ethylacrylamide; N-(3-Methoxypropyl)acrylamide; 2-hydroxyethylmethacrylate(HEMA); 2-hydroxyethyl acrylate (HEA); hydroxypropyl acrylate;hydroxypropyl methacrylate (HPMA);N-[Tris(hydroxymethyl)methyl]acrylamide; trimethylammonium 2-hydroxypropylmethacrylate hydrochloride; dimethylaminoethyl methacrylate(DMAEMA); glycerol methacrylate (GMA); N-vinyl-2-pyrrolidone (NVP);dimethylaminoethyl methacrylamide; (meth)acrylamide; allyl alcohol;vinyl pyridine; N-(1,1-dimethyl-3-oxobutyl)acrylamide; acrylic acid(AA); methacrylic acid (MAA);N-(2-methacryloyloxy)ethyl-N,N-dimethylamino propane sulfonate;N-(3-methacryloylimino)propyl-N,N-dimethylammino propane sulfonate;N-(3-methacryloylimino)propyl-N,N-dimethylammino propane sulfonate;2-(methacryloyloxy)ethyl phosphatidylcholine and 3-(2′-vinyl-pyridinio)propane sulfonate, 6-O-vinylsebacyl-D-glucose, fructose methacrylate,glucose methacrylate, ribose methacrylate, mannitol methacrylate,sorbitol methacrylate, methacrylated oligosaccharides, methacrylatedoligo-fructose, 2-Acetoacetoxy-ethyl Methacrylates, TetrahydrofurfurylMethacrylates; 2-Hydroxyethyl Methacrylates/Succinates; 2-HydroxyethylMethacrylate Phosphates; Hepta-O-benzyl monomethacryloyl sucrose.

Examples of hydrophobic monomers include but are not limited to Methylmethacrylate; glycidyl methacrylate; ethyl methacrylate; butylmethacrylate; hexyl methacrylate; tert-butyl methacrylate; cyclohexylmethacrylate; Isobornyl Methacrylates; 2-ethylhexyl methacrylate; heptylmethacrylate; octal methacrylate; Lauryl methacrylate;2,2,2-trifluoroethyl methacrylate; 1,1-dihydroperfluoroethylacrylate;1H,1H,7H-dodecafluoroheptyl acrylate; hexafluoroisopropyl acrylate;1H,1H,2H,2H-heptadecafluorodecyl acrylate; pentafluorostyrene;trifluoromethyl styrene; pentafluoroethyl acrylate; pentafluoroethylmethacrylate; hexafluoroisopropyl acrylate; hexafluoroisopropylmethacrylate (HFIPMA); methacrylate-functionalized fluorinatedpolyethylene oxides; 3-Methacryloxypropyl Tris-(Trimethylsiloxy) Silane;3-Methacryloxypropyl Tris-(Trimethylsiloxy) Silane;Methacryloxyethoxytris-(Trimethylsiloxy) Silane; TrimethylsilylmethylMethacrylate; 1H,1H,11H-Eicosafluoroundecyl Methacrylate;1H,1H,9H-Hexadecafluorononyl Acrylate; 4-Vinylbenzyl HexafluoroisopropylEther; Pentafluorobenzyl Acrylate; Pentafluorobenzyl Methacrylate;Perfluorocyclohexyl Methyl Acrylate; PerfluorocyclohexylmethylMethacrylate; m-Fluorostyrene; and the like.

Examples of Amphiphilic Monomers include but are not limited to2-Methoxyethoxyethyl Methacrylates; Ethoxyethyl Methacrylates;2-(dimethylamino)ethyl methacrylate; 2-(diethylamino)ethyl methacrylate;N-[3-(Dimethylamino)-propyl]acrylamide;N-[3-(Dimethylamino)propyl]meth-acrylamide; Hydroxy oligo(ethyleneglycol)₆ methacrylate; Methoxy oligo(ethylene glycol)₈ methacrylate;N-(1,1-di(O—B-D-glucorpyranosyloxymethyl)-1-(undecyl carbamoyloxymethyl)methyl)acrylamide;5-acrylamido-5-undecylcarbamoyloxymethyl-2,2-dimethyl-cyclol, 3dioxahexane;N-(1,1-(2′,3′,4′6″tetra-O-acetyl-B-D-glucopyranosyloxy-methyl)-1-(undecylcarbamoyloxymethyl)-methyl)-acryl-amide; N-1,1-di(hydroxymethylmethyl)-1(undecylcarbamoyl Oxymethyl)-methyl)acrylamide; N-(1,1-(2, 3, 4,6-″tetra-O-acetyl-ft-D-glucopyranosyloxy-methyl)-1-(undecylcarbamoyloxymethyl)-methyl)-acryl-amide;(2-Hydroxy-3-Methacryloxypropyl) Trimethylammonium Chloride; acrylamidefunctionalized Polyetheramine such as Acrylamide derivatives ofpolyether amines Polyetheramines are available from Huntsman Chemicaland sold under the trade name “Jeffamine” (examples of polyether aminesinclude Jeffamine M-(600, 1000, 2005, 2070)

Acrylamide derivatives of polyether amines may be formed throughreaction of a polyetheramine with reagents such as methacrylic anhydrideor acryloyl chloride as shown in Scheme 2, where hydrophilic/lipophilicbalance (HLB) depends on values of X and Y and where X and Y are wholenumbers.

Zwitterionic Monomers include, but are not limited to,1-(3-Sulfopropyl)-2-Vinylpyridinium Betaine;N-(3-Sulfopropyl)-N-Methacryloxyethyl-N,N-Dimethylammonium Betaine; andN-(3-Sulfopropyl)-N-Methacryloylamidopropyl-N,N-DimethylammoniumBetaine.

Examples of antimicrobial monomers include but are not limited to 2(Methacryloyloxy)-ethyl]-trimethylammonium chloride;2-(methacryloxy)ethyl]dimethyl dodecyl ammonium chloride;2-(methacryloxy)ethyl]-dimethyl hexadecyl ammonium chloride;2-(methacryloxy)decyl]dimethyl hexadecyl ammonium chloride;2-(methacryloxy)-dodecyl]dimethyl hexadecyl ammonium chloride;2-(methacryloxy)hexadecyl]dimethyl hexadecyl ammonium chloride;[2-(methacryloxyethyl]azabicyclo[2.2.2]ammonium chloride;1-{2-[(2-methylprop-2-enoyl)oxy]ethyl}pyridin-1-ium chloride;1-{2-[(2-methylprop-2enoyl)oxy]decyl}pyridin-1-ium chloride;1-{2-[(2-methylprop-2-enoyl)oxy]dodecyl}pyridin-1-ium chloride;1-{2-[(2-methylprop-2-enoyl)oxy]hexadecyl}pyridin-1-ium chloride.

Examples of UV-Blockers include:2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate;2-{2′-Hydroxy-5′-(γ-propoxy)-3′-t-butylphenyl}-5-methoxy-2H-benzotriazole,2-(2H-Benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol; and1-(2-METHYL-ALLYL)-1H-BENZOTRIAZOLE;2-hydroxy-4-Acryloyloxy-benzophenone).

Examples of Blue Light Blockers include, but are not limited to, variousyellow and/or orange dyes. Examples of yellow dyes include but are notlimited to: N,N-bis-(2-allylcarbomatoethyl)-(4′-phenylazo) aniline;N,N-bis-(2-hydroxyethyl)-(4-phenylazo) aniline;N,N-bis-(2-vinylacetoxyethyl)-(4′-phenylazo)aniline; andN-2-[3′-2″-methylphenylazo)-4′-hydroxyphenyl]ethylvinylacetamide.Examples of orange dyes include but are not limited to: Reactive Orange16, Reactive Orange 13 (PROCION ORANGE H-2R), disperse orange 3acrylamide, disperse orange 3 meth-acrylamide, disperse orange 3acrylate, disperse orange 3 methacrylate, disperse orange 25 acrylamide,disperse orange 25 methacrylamide, disperse orange 25 acrylate, anddisperse orange 25 methacrylate, Reactive orange dye containing vinylsulfone.

Solvents include, but are not limited to: alcohols such as methanol,ethanol, isopropanol, 1-propanol, n-butanol, tertbutyl alcohol, t-amylalcohol; Isoamyl alcohol; Benzyl alcohol; 2-Ethylhexanolethyleneglycol,propylene glycol; ethyl lactate, cyclopentanone, 2-ethoxyethanol,glycerin, 2-Butoxyethanol; Propylene Glycol Monomethyl Ether; DecylAlcohol; Cyclohexanol; Diethylene glycol monobutyl ether; Glymes such asEthylene glycol dimethyl ether; Ethylene glycol diethyl ether;Diethylene glycol dimethyl ether; Dipropylene glycol dimethyl ether;Diethylene glycol dibutyl ether; Poly(ethylene glycol) dimethyl ether;Tetraethylene glycol dimethyl ether; Ethyl Acetate; Propyl Acetate;n-Butyl Acetate; t-Butyl Acetate; Propylene carbonate; Dimethylcarbonate; Diethyl carbonate; 2 Ethylhexyl Acetate; Butyrolactone;Acetone, methyl ethyl ketone, cyclopentanone; cyclohexanone;2-heptanone, -methyl-2-hexanone; Acetyl acetone; Ethyl propionate;Methyl isobutyl ketone; 2-Butoxyethanol acetate; Bis(2-ethylhexyl)adipate; Methyl phenyl acetate; Methyl lactate; Hexyl acetate; Dimethylform amide, N-methylpyrolidone, 2-Methyl-tetrahydrofuran; N,N-dimethyllactamide, Tetrahydrothiophene (Sulfolane), acetamide, dimethylacetamide. Mixtures formed by combining two or more of the solvents canalso be used.

Also disclosed herein are UV-blocking actinically-crosslinkablepolysiloxane-polyglycerol block copolymers comprising any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdisclosed herein and a UV-blocker.

Also disclosed herein are blue-light blocking actinically-crosslinkablepolysiloxane-polyglycerol block copolymers comprising any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein and a blue light blocker.

Also disclosed herein are interpenetrating polymer networks. An“interpenetrating polymer network” (IPN) as used herein refers broadlyto an intimate network of two or more polymers at least one of which iseither synthesized and/or crosslinked in the presence of the other(s).Techniques for preparing IPN are known to one skilled in the art. For ageneral procedure, see U.S. Pat. Nos. 4,536,554; 4,983,702; 5,087,392;and 5,656,210, the contents of which are all incorporated herein byreference.

In some examples, the interpenetrating polymer networks comprise theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein crosslinked with a crosslinker in the presence of aninitiator (e.g., a photo-initiator, a thermal initiator), a hydrophilicmonomer, a hydrophobic monomer, an amphiphilic monomer, a zwitterionicmonomer, a UV-blocker, a blue light blocker, an antimicrobial monomer, adye, a pigment, a solvent, or a combination thereof.

Suitable photo-initiators include, but are not limited to, acetophenone;anisoin; anthraquinone; benzoin; benzoin methyl ether; benzoin ethylether; benzoin isobutyl ether; diethoxyacetophenone; benzoylphosphineoxide; 1-hydroxycyclohexyl phenyl ketone; 50/50 blend ofBenzophenone/1-Hydroxycyclohexyl phenylketone; 2,2-Diethoxyacetophenone;4,4′-Dihydroxybenzophenone; 2,2-Dimethoxy-2-phenylacetophenone;4-(Dimethylamino)-benzophenone; 4,4′-Dimethyl-benzyl;2,5-Dimethylbenzophenone; 3,4-Dimethylbenzophenone;Diphenyl(2,4,6-trimethylbenzoyl)phosphineoxide/2-Hydroxy-2-methylpropiophenone; 50/50 blend;4′-Ethoxyacetophenone; 3′-Hydroxyacetophenone; 4′-Hydroxyacetophenone,3-Hydroxybenzophenone; 4-Hydroxybenzophenone; 1-Hydroxycyclohexyl phenylketone; 2-Methyl-4′-(methylthio)-2-morpholinopropiophenone;Phenanthrenequinone, 4′-Phenoxy-acetophenone; Thioxanthen-9-one;DARACURE® types (e.g., DARACURE® 1173); Irgacure® types (e.g., Irgacure1173 and Irgacure® 2959); and UV/visible light photo initiators(Available from Spectra Group and sold under the trade names H-Nu 470,H-Nu 535, H-Nu 635).

Examples of thermal initiators include, but are not limited to, azo typeinitiators such as: 2,2′-azobis(2,4-dimethylpentanenitrile),2,2′-azobis(2-methylpropanenitrile), 2,2′-azobis(2-methylbutanenitrile),Azobisisobutyronitrile (trade name VAZO 64);2,2′-Azodi(2-methylbutyronitrile) (trade name VAZO 67);2-2′-Azobis(2,4-dimethylvaleronitrile) (trade name VAZO 52); and1,1′-Azobis(cyanocyclohexane) (trade name VAZO 88). In some examples,the thermal initiator is 2,2′-Azobis-(isobutyronitrile) (AIBN). Oneskilled in the art will recognize that polymerization and curing offormulations containing azo type initiators can also be triggered withUV-light.

Other types of initiators include organic peroxy compounds such as:benzoyl peroxide; tert-Butyl hydro peroxide; tert-Butyl per acetate,t-butyl peroxyneodecanoate; t-butyl peroxypivalate; tertiary-butylperoxyisopropyl carbonate; cumene hydro peroxide;2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne; Dicumyl peroxide;2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane;2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane;1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane;1,1-Bis(tert-butylperoxy)cyclohexane; tert-Butyl peroxide; Laurylperoxide and the like. Many peroxy based initiators are sold under thetrade name Luperox and are available from ARKEMA.

In some examples, two or more of the various types of initiators can becombined in the compositions described herein. For example, thecompositions can comprise a combination of one or more thermal initiatorand one or more photo-initiator. Compositions comprising both a thermalinitiator and a photo-initiator can be subjected to both photocuring(e.g., with UV light) and thermal curing. For example, the compositioncan be partially cured with UV light followed by thermal curing and postcuring.

In some examples, the silicone hydrogel compositions described hereincomprise the crosslinked polysiloxane-polyglycerol block copolymers andoptionally one or more monomers, polymers, or macromers. The choice ofmonomer, polymer, or macromer depends, in part, on the desired structureof the polymer network. Therefore, one might select hydrophilicmonomers, hydrophobic monomers, amphiphilic monomers, or combinationsthereof in view of the desired structure. The actinically cross-linkablepolysiloxane-polyglycerol block copolymers with actinically curablepolyglycerol branches can increasing the compatibility of the siliconehydrogel compositions prepared therefrom with various hydrophobicmonomers and hydrophilic monomers.

In some examples, the silicone hydrogel compositions described hereincan further comprise one or more monomer units selected from the groupconsisting of N-vinyl-2-pyrrolidone (NVP), N,N-dimethyl acrylamide(DMA), dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,vinyl acetate, 2-Hydroxyethyl methacrylate (HEMA), glycerolmono-methacrylate (GMMA), N-Hydroxyethyl acrylamide (NHA),N-(2,3-Dihydroxypropyl)acrylamide (NDHA), N-(hydroxyl methyl)acrylamidesolution (NHMA), N-[3-(Dimethylamino)propyl]methacrylamide, aC₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight averagemolecular weight of from 300 to 2000, N-vinyl-N-methyl isopropyl amide,N-vinyl-N-methyl acetamide, and mixtures thereof.

The silicone hydrogel compositions described herein comprising theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein crosslinked with a crosslinker can exhibit improvedproperties. For example, the silicone hydrogel compositions can providean improvement over hydrogels in which the hydrophilicity ofpolydimethylsiloxane copolymers was improved by attaching PEG chains toPDMS (e.g., as described by U.S. Pat. Nos. 8,231,218, 8,552,085, and9,804,417). The use of polysiloxane prepolymers, such as polydimethylsiloxane, with polyglycerol branches described herein provides thefollowing advantages over PDMS-PEG: The polyglycerol repeat units aremore hydrophilic than PEG due to the presence of one OH group per repeatunit in the polyglycerol. The OH rich polyglycerol chains are morereadily functionalized than PEG chains, which allows for thepolyglycerol units to be substituted with actinically curable groups,therefore allowing for UV cure in the production of contact lensesprepared from the actinically-crosslinkable polysiloxane-polyglycerolblock copolymers described herein. The OH functionality in polyglycerolrepeat units also allows such copolymers to be cross-linked with avariety of crosslinkers, such as difunctional isocyanates, epoxies,alkyl halides, and aldehydes. Another potential advantage of materialsdescribed in this invention is improved thermal oxidative stability ascompared to PDMS-PEG (Siegers et al. Chemistry A European Journal, 2004,10(11), 2831-2838). Thermal oxidative stability of polyglycerol units isrelatively high compared to PEG. Thermal degradation of linearpolyglycerol starts at 250° C. (Atkinson et al. Macromol. Chem. Phys.2011, 212(19), 2103-2113), while heating PEG at 80° C. in air results indegradation reactions which produce esters and formic esters (Chongyoupet al. Polymer, 1997, 38(2), 317-323). In some examples, thepolyglycerol is useful as an internal wetting agent for contact lensescomprising the silicone hydrogel compositions, such that the contactlenses derived from the silicone hydrogel compositions exhibithydrophilic surfaces without the need for post-curing surface treatmentdue to the presence of the polyglycerol side chains in thepolysiloxane-polyglycerol block copolymers.

Devices and Methods of Use

Also disclosed herein are methods of use of any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymers andsilicone hydrogels described herein.

For example, also described herein are methods of use of any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymers andsilicone hydrogels described herein in medical devices and ophthalmicapplications such as contact lenses.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers and silicone hydrogelsdescribed herein can be used in the construction of co-continuousbiphasic or multiphasic materials.

The methods of use can, for example, comprise using theactinically-crosslinkable polysiloxane-polyglycerol block copolymersand/or the silicone hydrogel compositions described herein in theconstruction of medical devices, coatings for medical devices and avariety of biomedical applications. For example, the methods of use cancomprise using the actinically-crosslinkable polysiloxane-polyglycerolblock copolymers, the silicone hydrogel compositions, and/or theinterpenetrating polymer networks described herein as hydrophiliccoatings for any number of medical devices including, but not limited tocatheters, contact lenses, endoscopes, cell growth platforms,microfluidic devices, body implants, coatings for implants that comeinto contact with tissue (e.g., epithelial tissue, connective tissue,muscle tissue, and nerve tissue) and biological fluids (e.g., blood,mucus, urine, tears, saliva, amniotic fluid, synovial fluid). Themethods of use can, in some examples, comprise applying theactinically-crosslinkable polysiloxane-polyglycerol block copolymersand/or the silicone hydrogel compositions described herein to any lensmaterial including hydrogels and silicone hydrogels and rigid gaspermeable lenses (RGP's) to thereby render the lens materialhydrophilic.

Examples of lens materials that can be rendered hydrophilic include, butare not limited to, avefilcon A, acofilcon A, acofilcon B, acquafilconA, alofilcon A, alphafilcon A, amfilcon A (reclassified to ocufilconseries), astifilcon A, atlafilcon A, balafilcon A, bisfilcon A, bufilconA, comfilcon A, crofilcon A, cyclofilcon A, darfilcon A, delefilcon A,deltafilcon A, deltafilcon B, dimefilcon A, droxifilcon A, efrofilcon A,elastofilcon A, enfilcon A, epsiflcon A, esterifilcon A, etafilcon A,galyfilcon A, genfilcon A, govafilcon A, hefilcon A, hefilcon B,hefilcon C, hefilcon D, hilafilcon A, hilafilcon B, hioxifilcon A,hioxifilcon B, hioxifilcon C, hioxifilcon D, hydrofilcon A, iberfilconA, lenefilcon A, licryfilcon A, licryfilcon B, lidofilcon A, lidofilconB, lotrafilcon A, lotrafilcon B, mafilcon A, mesifilcon A, methafilconB, mipafilcon A, narafilcon A, narafilcon B, nelfilcon A, nesofilcon A,netrafilcon A, ocufilcon A, ocufilcon B, ocufilcon C, ocufilcon D,ocufilcon E, ocufilcon F, ofilcon A, omafilcon A, oxyfilcon A,pentafilcon, perfilcon A, petrafocon A-hem-larafilcon A, pevafilcon A,phemfilcon A, phemfilcon B, polymacon A, senofilcon A, shofilcon A,sifilcon A, silafilcon, siloxyfilcon A, surfilcon, tasfilcon, tefilcon,tetrafilcon A, trifilcon, uvifilcon, vasurfilcon A, vifilcon A, vifilconB, and xylofilcon A.

In some examples, the methods of use can comprise using theactinically-crosslinkable polysiloxane-polyglycerol block copolymers,the silicone hydrogel compositions, and/or the interpenetrating polymernetworks described herein in a range of cell culture applications forthe expansion and directed differentiation of various cell types byacting as extracellular matrix mimics for 3D Cell Culture.

The methods of use can, for example, comprise using theactinically-crosslinkable polysiloxane-polyglycerol block copolymers,the silicone hydrogel compositions, and/or the interpenetrating polymernetworks described herein as synthetic matrixmetallo-proteinase-sensitive materials for the conduction of tissueregeneration.

In some examples, the methods of use can comprise using theactinically-crosslinkable polysiloxane-polyglycerol block copolymers,the silicone hydrogel compositions, and/or the interpenetrating polymernetworks described herein as micro-valves and/or micro-pumping devicesdue to the propensity of the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers, the silicone hydrogelcompositions, and/or the interpenetrating polymer networks to absorblarge volumes aqueous and/or non-aqueous fluids coupled with theresponse of the actinically-crosslinkable polysiloxane-polyglycerolblock copolymers, the silicone hydrogel compositions, and/or theinterpenetrating polymer networks to various forms of stimulation (e.g.,pH, electrical current, temperature, ionic strength).

The actinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein can, for example, be used to make soft (hydrophilic)contact lenses with or without decorative print patterns (e.g., softcontact lenses that are optionally cosmetically tinted). For example,soft contact lenses that are cosmetically tinted can be prepared fromformulations comprising the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers described herein and a dyeand/or a pigment.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers and silicone hydrogelsdescribed herein can be used as a contact lens, wherein theactinically-crosslinkable polysiloxane-polyglycerol block copolymers arederived from a polysiloxane prepolymer comprising a polyglycerol sidechain and the polyglycerol is useful as an internal wetting agent forcontact lenses comprising the silicone hydrogel compositions, such thatthe contact lenses derived from the silicone hydrogel compositionsexhibit hydrophilic surfaces without the need for post-curing surfacetreatment due to the presence of the polyglycerol side chains in thepolysiloxane-polyglycerol block copolymers.

Also disclosed herein are articles of manufacture and devices comprisingany of the actinically-crosslinkable polysiloxane-polyglycerol blockcopolymers, silicone hydrogels, and/or interpenetrating polymer networksdescribed herein. The article of manufacture can, for example, comprisean ophthalmic device (e.g., contact lens, intraocular lens, cornealinlay, corneal ring) or membrane. Such articles of manufacture anddevices can be fabricated by methods known in the art.

In some examples, the article of manufacture can comprise a membraneprepared from the silicone hydrogel compositions described herein. Themembrane can, for example, allow for efficient permeation of smallmolecules and ions. In some examples, the contact lens or membrane canallow for efficient transport of water, ions, oxygen, and nutrients andare therefore well suited for use as ophthalmic devices such as contactlenses. In some examples, the article of manufacture can comprise anophthalmic device (e.g., contact lens, intraocular lens, corneal inlay,corneal ring) obtained from a lens-forming material including theactinically-crosslinkable polysiloxane-polyglycerol block copolymers andoptionally a hydrophilic monomer and/or hydrophobic monomer.

In some examples, the article of manufacture can comprise a contact lenscomprising the silicone hydrogel compositions described herein, whereinthe contact lens can exhibit an improved lubricous surface having wearpermanence, combined with the characteristics of biocompatibility and alow coefficient of friction in contact with tear fluid.

Also described herein are silicone hydrogel contact lenses obtained byactinically cross-linking the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer, wherein theactinically-crosslinkable polysiloxane-polyglycerol block copolymercomprises a methacrylated polydimethylsiloxane-polyglycerol blockcopolymer. The silicone hydrogel contact lens can comprises: a siliconehydrogel material and hydrophilic polymer branches which are covalentlyanchored to the polymer matrix of the silicone hydrogel material,wherein the silicone hydrogel material is obtained by polymerizing alens-forming material including the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers described herein, wherein thepolyglycerol side chains in the silicone hydrogel material are capableof imparting the silicone hydrogel contact lens with a hydrophilicsurface without post-curing surface treatment. This contrasts withsilicone hydrogel materials other than those described herein andcontact lenses prepared therefrom, which typically require a post-curingsurface treatment to render the surface hydrophilic.

For example, silicone hydrogel materials other than those describedherein typically have a surface or at least a portion of its surfacewhich is hydrophobic (non-wettable). Hydrophobic surfaces or portions ofsurfaces that are hydrophobic will up-take lipids or proteins. In thecase where the silicone hydrogel materials are used as contact lenses,such hydrophobic surfaces or portions of surfaces that are hydrophobicwill up-take lipids or proteins from the ocular environment and canadhere to the eye. Thus, a silicone hydrogel contact lens will generallyrequire a surface modification which is typically carried out aftercast-molding of the lens.

On the other hand, when a liquid lens forming material including theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein is introduced in a mold for making a contact lens, theactinically curable groups linked to the polysiloxane prepolymer arehydrophilic (e.g., they comprise actinically curable hydrophilic polymerchains) and can be adsorbed at the interface between the mold and thelens forming material. When the actinically curable hydrophilic polymerchains are present in a sufficient amount, interfacial films comprisingthe hydrophilic polymer chains can be formed with an adequate thicknessat the mold-liquid interface prior to curing (polymerization), and theinterfacial films can be subsequently preserved after curing.

The silicone hydrogel contact lenses prepared from the compositionsdescribed herein can, for example, have an Ionoflux DiffusionCoefficient, D, of 2.0×10⁻⁶ mm²/min or more (e.g., 4.0×10⁻⁶ mm²/min ormore, 9.0×10⁻⁶ mm²/min or more, 1×10⁻⁵ mm²/min or more, or 5×10⁻⁵mm²/min or more).

The silicone hydrogel contact lenses prepared from the compositionsdescribed herein can, for example, have a high oxygen permeability. Forexample, the silicone hydrogel contact lenses prepared from thecompositions described herein can have an apparent oxygen permeabilityof 35 barrers or more (e.g., 40 barrers or more, 50 barrers or more, 60barrers or more, 70 barrers or more, or 80 barrers or more).

The silicone hydrogel contact lenses prepared from the compositionsdescribed herein can, for example have an elastic modulus of 0.25 MPa ormore (e.g., 0.3 MPa or more, 0.4 MPa or more, 0.5 MPa or more, 0.6 MPaor more, 0.7 MPa or more, 0.8 MPa or more, 0.9 MPa or more, 1 MPa ormore, 1.1 MPa or more, 1.2 MPa or more, 1.3 MPa or more, 1.4 MPa ormore, 1.5 MPa or more, or 1.6 MPa or more). In some examples, thesilicone hydrogel contact lenses prepared from the compositionsdescribed herein can have an elastic modulus of 1.75 MPa or less (e.g.,1.7 MPa or less, 1.6 MPa or less, 1.5 MPa or less, 1.4 MPa or less, 1.3MPa or less, 1.2 MPa or less, 1.1 MPa or less, 1 MPa or less, 0.9 MPa orless, 0.8 MPa or less, 0.7 MPa or less, 0.6 MPa or less, or 0.5 MPa orless). The elastic modulus of the silicone hydrogel contact lensesprepared from the compositions described herein can range from any ofthe minimum values described above to any of the maximum valuesdescribed above. For example, the silicone hydrogel contact lensesprepared from the compositions described herein can have an elasticmodulus of from 0.25 MPa to 1.75 MPa (e.g., from 0.25 MPa to 1 MPa, from1 MPa to 1.75 MPa, from 0.25 MPa to 0.75 MPa, from 0.75 MPa to 1.25 MPa,from 1.25 MPa to 1.75 MPa, from 0.5 MPa to 1.25 MPa, or from 0.75 MPa to1 MPa).

The silicone hydrogel contact lenses prepared from the compositionsdescribed herein can, for example, have a water content of 15% or more(e.g., 20% or more, 25% or more, 30% or more, 35% or more, 40% or more,45% or more, 50% or more, 55% or more, 60% or more, 65% or more, or 70%or more). In some examples, the silicone hydrogel contact lensesprepared from the compositions described herein can have a water contentof 80% or less (e.g., 75% or less, 70% or less, 65% or less, 60% orless, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less,30% or less, or 25% or less). The water content of the silicone hydrogelcontact lenses prepared from the compositions described herein can rangefrom any of the minimum values described above to any of the maximumvalues described above. For example, the silicone hydrogel contactlenses prepared form the compositions described herein can have a watercontent of from 15% to 80% (e.g., from 15% to 45% from 45% to 80%, from15% to 30%, from 30% to 45%, from 45% to 60%, from 60% to 80%, from 25%to 8%, from 15% to 60%, or from 25% to 70%).

The silicone hydrogel contact lenses prepared from the compositionsdescribed herein can, for example, have an averaged water contact angleof 70 degrees or less (e.g., 65 degrees or less, 60 degrees or less, 55degrees or less, 50 degrees or less, 45 degrees or less, 40 degrees orless, 35 degrees or less, 30 degrees or less, 25 degrees or less, 20degrees or less, 15 degrees or less, or 10 degrees or less).

The silicone hydrogel contact lenses prepared from the compositionsdescribed herein can, in some examples, further comprise asilicone-containing vinylic monomer, a silicone-containing macromer, asilicone-containing prepolymer, a hydrophilic vinylic monomer, ahydrophobic vinylic monomer, a hydrophilic prepolymer, a cross-linkingagents, an antimicrobial agent, a chain transfer agent, radicalinitiator, a UV-absorber, an inhibitor, a filler, a visibility tintingagent, a bioactive agent, a leachable lubricant, or a combinationthereof.

In some examples, the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers described herein comprise twoor more polymeric chains (blocks), which are structurally different andchemically bonded to each other. Under certain conditions, theactinically-crosslinkable polysiloxane-polyglycerol block copolymers cansegregate into a variety of ordered structures.

In some examples, ordered block copolymer structures are substantiallylocked in place through chemical reactions such as cross-linking ofactinically curable groups (FIG. 3 ), substitution reactions, additionreactions, “click reactions”, polymerization reactions or any number ofchemical reactions known in the art. In one some examples, blockcopolymers comprising PDMS with cross-linkable polyglycerol branches areself-assembled in polar solvent and/or polar monomer(s) to form vesicleshaving bi-continuous or multiphasic structures. In certain examples,polymerization induced self-assembly (PISA) is achieved bypolymerization of monomer solutions containing theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein.

These ordered structures with bi-continuous phases are particularly wellsuited to uses and devices when two fundamentally different propertiesare required from the same material. For example, bi-continuousmaterials can be used in the area of polymer electrolyte membranes whichrequire efficient transport of ions and simultaneously resilientmechanical properties. In the case of polyelectrolytes, the presence ofa continuous phase suitable for uninterrupted ion-conducting pathwayswhile also having a second phase that can provide mechanical strength isdesirable. Bi-continuous materials can also be used in cases requiringmass transfer of chemical species having significantly differentphysical or chemical properties (e.g., solubility, polarity, non-polar,acidity, basicity, pharmacologically activity, molecular size/MW,boiling physical state (gas, liquid, solid)). For example, it can bedesirable to have one phase that is suitable for mass transfer ofhydrophilic species while having a second phase that is suitable formass transfer of lipophilic species. In certain applications, it isdesirable to have materials that are capable of efficient mass transferof gaseous substances, liquid substances, and solid substances. Forexample, a wound dressing capable of efficient mass transfer of oxygen,antimicrobial agents, antifungal agents, and antiviral agents, fluid(e.g. liquor puris), and gases (oxygen, CO₂) would be highly effectivein facilitating wound healing.

Examples of antimicrobial agents include but are not limited to(neomycin, bacitracin, Penicillin, Penicillin G, Amoxicillin,Ampicillin, Cloxacillin, Methicillin, Amoxicillin+Clavulanate(Augmentin), Ticarcillin+Clavulanate, Nafcillin, Cefuroxime, LackingUrine, Cefotaxime, Cefoperazone, Cephtriaxone, Cefepime, Tetracycline,Minocycline, Doxycycline, Azithromycin, Erithromycin, Clarithromycin,Clindamycin, Sulfamethoxazole-Trimethoprim, Ciprofloxacin (Cipro),Norfloxacin, Ofloxacin, Levofloxacin, Streptomycin, Tobramycin,Gentamycin, Amikacin). Examples of antifungal agents include but are notlimited to (Amphotericin B, Candicidin, Bifonazole, Albaconazole,Amantadine, Amprenavir, Atazanavir, Efavirenz, Ibacitabine, Umifenovir,Abafungin, Ciclopirox, Norvir, Peramivir, Podophyllotoxin, Saquinavir,Sofosbuvir). Examples of antiviral agents include but are not limited to(Acyclovir, Trifluridine, Zanamivir, Ribavirin, Tenofovir,Tromantadine).

Bi-continuous or multi-continuous multiphasic materials can also be usedin cases that require mass transfer of one or more of the followingtypes of species: ionic species, gases, oxygen, pharmacologically activesubstances, biomolecular species, and fluids. Examples of ionic speciesinclude but are not limited to potassium salts, sodium salts, calciumsalts, magnesium salts, silver salts, copper salts, iron salts, aluminumsalts, chloride salts, bromide salts, fluoride salts, iodide salts,Sulphur salts, phosphate salts, and borate salts. Examples of gasesinclude but are not limited to CO₂, NO (nitric oxide), N₂O (nitrousoxide), NO₂ (nitrogen dioxide), water vapor, O₂, O₃, NH₃, borontri-fluoride (BF₃), sulfur hexafluoride (SF₆), silane (SiH₄), silicontetrachloride (SiCl₄), silicon tetrafluoride (SiF₄), PH₃, phosgene(COCl₂), carbon monoxide (CO), sulfur dioxide (SO₂), methane (CH₄),ethane (C₂H₆), propane (C₃H₈), cyclopropane (C₃H₆), butane (C₄H₁₀),cyclobutane (C₄H₈), acetylene, chlorine, fluorine, argon, neon, krypton,radon, xenon, hydrogen cyanide, hydrogen sulfide, HCl, HF, HBr, nitrogen(N₂), hydrogen (H₂), chlorofluorocarbons (CFCs), andhydro-chlorofluorocarbons (HCFCs).

The actinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein comprise one or more polyglycerol branches tethered toa polysiloxane (e.g., PDMS) main chain. Because the hydrophilicpolyglycerol branches are chemically anchored to the polysiloxanechains, contact lenses and membranes produced from these materials havelubricity that is more resistant to failure or variation in lubricityduring use than contact lenses prepared from other silicone hydrogelmaterials.

For example, contact lenses and membranes prepared from theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein can exhibit improved properties over contact lenses andmembranes wherein surface lubricity was improved using PDMS bearing PEGchains (e.g., as described in U.S. Pat. Nos. 8,231,218, 8,552,085, and9,804,417), because PEG is prone to oxidative degradation as discussedabove. Contact lenses and membranes produced from theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein are also an improvement over contact lenses andmembranes prepared using PDMS bearing PVP chains (e.g., as described inU.S. Pat. No. 6,367,929), because PVP can leach from those siliconehydrogel lenses.

Furthermore, the actinically-crosslinkable polysiloxane-polyglycerolblock copolymers described herein can have an amphiphilic nature due tothe polysiloxane prepolymer which can be hydrophobic and thepolyglycerol side chains which can be hydrophilic. The amphiphilicnature of the actinically-crosslinkable polysiloxane-polyglycerol blockcopolymers described herein can facilitate microscopic phase separationin a silicone hydrogel material prepared therefrom into a silicone-richmicroscopic phase and a hydrophilic microscopic phase. With theexistence of a co-continuous bi-phase structure (in microscopic scale),the silicone hydrogel material can have relatively high oxygen and ionpermeability's.

The actinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein comprising actinically cross-linkable groups located onthe polyglycerol grafts can be used to prepare silicone hydrogels withexcellent wettability. In addition, it was long thought that oxygenpermeability, Dk, of a silicone hydrogel contact lens and a non-siliconehydrogel contact lens would be approximately the same if both types oflenses had a water content of ≥70% (Morgan et al. Cont. Lens AnteriorEye 1998, 21, 3-6; Sweeney et al. Contact Lens Spectrum, Feb. 1, 2006;Jones, Contact Lens Spectrum, September 2002). Further, it waspreviously thought that in order for a silicone hydrogel contact lens tohave a Dk of ≥60 barrer, the silicone hydrogel lens would need to have awater content of 45% or less or 80% or more. However, certain siliconehydrogel compositions described herein have a Dk of 90 barrer and watercontent of 66%, showing that previous notions regarding siliconehydrogel Dk and water content were incomplete.

Methods of Making

Also described herein are methods of making theactinically-crosslinkable polysiloxane-polyglycerol block copolymers,the silicone hydrogel compositions, and/or the interpenetrating polymernetworks described herein, and the devices comprising theactinically-crosslinkable polysiloxane-polyglycerol block copolymers,the silicone hydrogel compositions, and/or the interpenetrating polymernetworks described herein.

For example, the actinically-crosslinkable polysiloxane-polyglycerolblock copolymers can be prepared by contacting a polysiloxane polymercomprising a polyglycerol side chain with a catalyst and a cure groupprecursor (e.g., an ethylenically unsaturated reagent).

Any suitable catalyst can be used to facilitate reactions of PDMS-PGLYwith the cure group precursor (e.g., anhydrides and otherfunctionalizing agents). For example, small molecule catalysts such astriethyl amine, pyridine, dimethylaminopyridine (DMAP), anddibutyltindilaurate (DBTDL) can be used. In some examples, smallmolecule catalysts can be replaced by polymer supported catalysts. Forexample, polystyrene supported DMAP can be used as a catalyst. Theadvantage of a polymer supported catalyst is the ease of separation fromreaction products.

Any number of other ethylenically unsaturated reagents may be used as acure group precursor to produce the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers. For example, the cure groupprecursor can comprise maelic anhydride, methacrylic anhydride,2-isocyanatoethylmethacrylate (IEM), acryloyl chloride, allylbromide,allylchloride, vinylbenzylchloride, or ethylenically activated esters(e.g., N-Acryloxy succinimide, N-(Methacryloxy)succinimide).

In some examples, actinically-crosslinkable polysiloxane-polyglycerolblock copolymers defined by Formula I can be prepared using the methodillustrated in Scheme 3 by contacting a polysiloxane polymer comprisinga polyglycerol side chain with a cure group precursor and optionally acatalyst.

In some examples, actinically-crosslinkable polysiloxane-polyglycerolblock copolymers defined by Formula IX can be prepared using the methodillustrated in Scheme 4 by contacting a polysiloxane polymer comprisinga polyglycerol side chain with a dimethylaminopyridine (DMAP) catalystand maelic anhydride as the cure group precursor. Use of maleicanhydride provides an added advantage of not producing a small moleculebi-product as is the case with linear anhydrides.

In some examples, actinically-crosslinkable polysiloxane-polyglycerolblock copolymers defined by Formula X can be prepared using the methodillustrated in Scheme 5 by contacting a polysiloxane polymer comprisinga polyglycerol side chain with a DMAP catalyst and methacrylic anhydrideas a cure group precursor.

In some examples, actinically-crosslinkable polysiloxane-polyglycerolblock copolymers defined by Formula XI can be prepared using the methodillustrated in Scheme 6 by contacting a polysiloxane polymer comprisinga polyglycerol side chain with dibutyltindilaurate (DBTDL) or othersuitable catalyst and 2-isocyanatoethylmethacrylate (IEM) as a curegroup precursor.

In some examples, the methods of making the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers can further comprisepreparing the polysiloxane polymer comprising a polyglycerol side chain.For example, a polysiloxane polymer comprising a polyglycerol side chaincan be prepared using the method illustrated in Scheme 7 by coupling athiol functionalized polydimethylsiloxane with an allyl substitutedpolyglycerol.

In some examples, the methods can further comprise preparing the allylsubstituted polyglycerol, for example through reaction of polyglyceroland allyl bromide with added catalyst (e.g., triethyl amine, pyridine,Pt, or DMAP) or without added catalyst. For example, the allylsubstituted polyglycerol can be prepared using the method illustrated inScheme 8.

In some examples, the methods of making the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers can further comprisepreparing the polysiloxane polymer comprising a polyglycerol side chain.For example, a polysiloxane polymer comprising a polyglycerol side chaincan be prepared using the method illustrated in Scheme 9 by coupling athiol functionalized polydimethylsiloxane with an allyl substitutedpolyglycerol (which can be prepared as illustrated in Scheme 8), wherethe catalyst can, for example, comprise Pt.

Under certain conditions, polysiloxane block copolymers bearingpolyglycerol side chains (or substituted polyglycerol side chains) cansegregate into a variety of ordered structures by the repulsion of theimmiscible blocks as shown in FIG. 1 -FIG. 3 .

In some examples, the ordered block copolymer structures can besubstantially locked in place through chemical reactions such ascross-linking of actinically curable groups (FIG. 3 ), substitutionreactions, addition reactions, “click reactions”, polymerizationreactions, or any number of chemical reactions known in the art. In someexamples, the actinically-crosslinkable polysiloxane-polyglycerol blockcopolymers comprising a polysiloxane (e.g., PDMS) with actinicallycross-linkable polyglycerol branches can self-assemble in a polarsolvent and/or in the presence of a polar monomer to form vesicleshaving bi-continuous or multiphasic structures. For example,polymerization induced self-assembly (PISA) can be achieved bypolymerization of monomer solutions containing theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein.

Also disclosed herein are methods for making heat stable bi-continuousphase membranes from the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers described herein, wherein theheat stable bi-continuous phase membranes have substantiallyuninterrupted ion-conducting conduits and uninterrupted oxygen transportchannels. The bi-continuous membrane structure can be locked in place orsubstantially locked in place through cross-linking reactions and/orpolymerization. The resulting materials can form vesicles in which theouter shell is comprised of polyglycerol chains while the inner core iscomprised of polysiloxane (e.g., polydimethylsiloxane) chains. Thevesicles can form aggregates which can then be cross-linked/polymerizedto yield stabilized structures suitable for use as contact lenses andvarious biomedical applications. The extent of self-assembly can bevaried by the addition of materials such as monomers, solvents, andpolymers. The extent of self-assembly can also be varied by the additionof various chemicals, changing pH, changing ionic strength, changingtemperature, and/or changing pressure. In some examples, the vesiclescan be inverted, disrupted, or damaged by a number of factors (e.g.,thermal stress, chemical stress, electrical stress, mechanical stresssuch as pressure, etc.). Vesicle stability can be influenced byenvironmental factors such as temperature and pressure, as well as bychemical composition (e.g., salts, solvents, monomers, buffers,polymers, bio-molecules). Therefore, such factors can increase ordecrease vesicle stability. The stability of the vesicles can beincreased or made substantially permanent by cross-linking reactions. Inhydrophilic solvents (e.g., polar solvents), the inner core of thevesicles will comprise hydrophobic domains (e.g., polysiloxane such asPDMS) while the outer shell will comprise hydrophilic domains (e.g.,polyglycerol). Decreasing the polarity of the chemical environmentthrough addition of substances that are more hydrophobic thanhydrophilic can lead to vesicles in which the outer shell compriseshydrophobic domains (e.g., polysiloxane such as PDMS) while the innercore comprises hydrophilic domains (e.g., polyglycerol). Uponcross-linking the outer shell, the inner core becomes trapped and doesnot migrate to the surface of the vesicle under contact lens useconditions. The cross-linking/polymerization can be achieved by a numberof means, such as photo-polymerization, typically in the presence of aphoto-initiator.

Also disclosed herein are methods of making silicone hydrogelcompositions, for example by crosslinking the actinically-crosslinkablepolysiloxane-polyglycerol block copolymers described herein. In someexamples, the method of making the silicone hydrogel compositions cancomprise mixing an initiator (e.g., photo-initiator, thermal initiator,or other suitable initiator) and a crosslinker with any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymers toform a mixture and crosslinking the mixture to form the (cross-linked)silicone hydrogel composition. The crosslinking can, for example, beperformed with the aid of any number of energy forms (e.g., thermalenergy, visible light energy, X-Rays, gamma rays, microwaves, ultrasonicenergy). In some examples, the crosslinking can comprise UV-curing(e.g., by UV irradiating the mixture) and the initiator can comprise aphoto-initiator. In the case of UV-curing, the use of thephoto-initiator is optional, however UV-curing in the absence of anadded photo-initiator is generally slow and inefficient.

Suitable photo-initiators include, but are not limited to, acetophenone;anisoin; anthraquinone; benzoin; benzoin methyl ether; benzoin ethylether; benzoin isobutyl ether; diethoxyacetophenone; benzoylphosphineoxide; 1-hydroxycyclohexyl phenyl ketone; 50/50 blend ofBenzophenone/1-Hydroxycyclohexyl phenylketone; 2,2-Diethoxyacetophenone;4,4′-Dihydroxybenzophenone; 2,2-Dimethoxy-2-phenylacetophenone;4-(Dimethylamino)-benzophenone; 4,4′-Dimethyl-benzyl;2,5-Dimethylbenzophenone; 3,4-Dimethylbenzophenone;Diphenyl(2,4,6-trimethylbenzoyl)phosphineoxide/2-Hydroxy-2-methylpropiophenone; 50/50 blend;4′-Ethoxyacetophenone; 3′-Hydroxyacetophenone; 4′-Hydroxyacetophenone,3-Hydroxybenzophenone; 4-Hydroxybenzophenone; 1-Hydroxycyclohexyl phenylketone; 2-Methyl-4′-(methylthio)-2-morpholinopropiophenone;Phenanthrenequinone, 4′-Phenoxy-acetophenone; Thioxanthen-9-one;DARACURE® types (e.g., DARACURE® 1173); Irgacure® types (e.g., Irgacure1173 and Irgacure® 2959); and UV/visible light photo initiators(Available from Spectra Group and sold under the trade names H-Nu 470,H-Nu 535, H-Nu 635).

Examples of thermal initiators include, but are not limited to, azo typeinitiators such as: 2,2′-azobis(2,4-dimethylpentanenitrile),2,2′-azobis(2-methylpropanenitrile), 2,2′-azobis(2-methylbutanenitrile),Azobisisobutyronitrile (trade name VAZO 64);2,2′-Azodi(2-methylbutyronitrile) (trade name VAZO 67);2-2′-Azobis(2,4-dimethylvaleronitrile) (trade name VAZO 52); and1,1′-Azobis(cyanocyclohexane) (trade name VAZO 88). In some examples,the thermal initiator is 2,2′-Azobis-(isobutyronitrile) (AIBN).

Other types of initiators include organic peroxy compounds such as:benzoyl peroxide; Luperox tert-Butyl hydro peroxide; tert-Butyl peracetate, t-butyl peroxyneodecanoate; t-butyl peroxypivalate;tertiary-butyl peroxyisopropyl carbonate; cumene hydro peroxide;2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne; Dicumyl peroxide;2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane;2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane;1,1-Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane;1,1-Bis(tert-butylperoxy)cyclohexane; tert-Butyl peroxide; Laurylperoxide and the like. Many peroxy based initiators are sold under thetrade name Luperox and are available from ARKEMA.

Cross-linkers include, for example, vinylic cross-linkers, difunctionalisocyanate cross-linkers, difunctional epoxide cross-linkers,difunctional alkyl halides (e.g., difunctional acid halides),difunctional-anhydrides, bis-halo-alky derivatives, activated esters, orany number of difunctional reagents capable for forming chemical bondswith polyglycerol OH groups.

Examples of vinylic cross-linkers include but are not limited to:Ethylene glycol dimethacrylate; Triethylene glycol dimethacrylate;Diethyleneglycol Dimethacrylate; 1,3-Glycerol Dimethacrylate;1,6-Hexanediol Dimethacrylate; 1,12-Dodecanediol Dimethacrylate;Trimethylolpropane Trimethacrylate; Poly (Ethyleneglycol) (400)Dimethacrylate; Isophorone Urethane Dimethacrylate;N,N′-Methylenebisacrylamide; 1,6-Hexamethylene bis-Methacrylamide;N,N′-Hexamethylenebismethacrylamide; N,N′-iso-Valerylidenebis-Methacrylamide;N,N′-Nonamethylenebisacrylamidem-Xylenebisacrylamide; 1,10-DecamethyleneGlycol Diacrylate; 1,2-Propanediol Diacrylate; 1,3-ButanediolDiacrylate; 1,3-Propanediol Diacrylate; 1,4-CyclohexanedimethylDiacrylate; 1,5-Pentanediol Diacrylate; 1,9-Nonanediol Diacrylate;2,2,3,3,4,4,5,5-Octafluoro-1,6-Hexanediol Diacrylate;2,2,3,3-Tetrafluoro-1,4-Butanediol Diacrylate; 2-Butene-1,4-Diacrylate;Aliphatic Urethane Acrylate in Tripropylene Glycol Diacrylate;Diethylene Glycol Diacrylate; Ethylene Diacrylate; neo-Pentyl GlycolDiacrylate; Sorbitol Diacrylate; Hexamethylene Diacrylate; ThiolDiethylene Glycol Diacrylate; Tetraethylene Glycol Diacrylate;Triethylene Glycol Diacrylate; Bisphenol A Glycidyl Methacrylate;Pentaerythritol Tetramethacrylate; 1,3-Divinyltetramethyl-disiloxane;3-Methacryloxypropyl Tris-(Vinyldimethylsiloxy) Silane;1,1,5,5-Tetrahydroperfluoro-1,5-Pentanediol Dimethacrylate;2,2,3,3,4,4,5,5-Octafluoro-1,6-Hexanediol Diacrylate;2,2,3,3,4,4,5,5-Octafluoro-1,6-Hexanediol Dimethacrylate.

Examples of difunctional isocyanate cross-linkers include but are notlimited to: Isophorone diisocyanate (IPDI), hexamethylene diisocyanate(HDI), methylene dicyclohexyl diisocyanate, toluene diisocyanate (TDI),Tolylene-2,4-diisocyanate, Tolylene-2,6-diisocyanate,trans-1,4-Cyclohexylene diisocyanate, Poly(propylene glycol), tolylene2,4-diisocyanate terminated, 1,4-Diisocyanatobutane,1,8-Diisocyanatooctane, 1,3-Bis(1-isocyanato-1-methylethyl)benzene,2,2,4-Trimethylhexamethylene Diisocyanate, 2,4,4-TrimethylhexamethyleneDiisocyanate, 1,4-Phenylene diisocyanate, 1,3-Phenylene diisocyanate,m-Xylylene diisocyanate, and methylenediphenyl diisocyanate (MDI).

Examples of difunctional epoxide cross-linkers include but are notlimited to: Bisphenol A diglycidyl ether, Glycerol diglycidyl ether,resorcinol diglycidyl ether, diglycidyl ether,bis(3,4-epoxycyclohexylmethyl) adipate, poly(ethylene glycol) diglycidylether, Bis[4-(glycidyloxy)phenyl]methane, 1,3-Butadiene diepoxide,1,4-Butanediol diglycidyl ether, 1,4-Butanediol diglycidyl ether,1,3-Butanediol diglycidyl ether, Bisphenol F diglycidyl ether, BisphenolA propoxylate diglycidyl ether, neopentyl glycol diglycidyl ether,N,N-Diglycidyl-4-glycidyloxyaniline, 4,4′-Isopropylidenediphenoldiglycidyl ether, Poly(propylene glycol) diglycidyl ether,Dicyclopentadiene dioxide, 1,2,5,6-Diepoxycyclooctane,1,2,7,8-Diepoxyoctane, Diglycidyl 1,2-cyclohexanedicarboxylate,3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate,2,5-bis[(2-oxiranylmethoxy)-methyl]-furan (BOF) and2,5-bis[(2-oxiranylmethoxy)methyl]-benzene, Poly(dimethyl siloxane),tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM),tri-glycidyl-aminophenol, e.3-(3-glycidoxypropyl)-1,1,1,3,5,5,5-heptamethyltrisiloxsane,1-epoxyethyl-3,4-epoxycyclohexane, 1,3,5-Triglycidyl isocyanurate,PC-1000 Epoxy Siloxane Monomer (available from Polyset), PC-1035 EpoxySiloxane Monomer (available from Polyset), Poly(dimethylsiloxane),diglycidyl ether terminated (average Mn ˜800, available from SIGMAALDRICH), epoxy terminated Poly(dimethylsiloxanes) available from ShinEtsu Silicone Company and sold under the trade names KF-105; X-22-163A;X-22-163B; X-22-163C; X-22-169AS; X-22-169B available from Shin EtsuSilicone Company; BIS[2-(3,4-EPOXYCYCLOHEXYL)-ETHYL2,4,6,8-Tetramethyl-2,4,6,8-tetrakis(propyl glycidylether)cyclotetrasiloxane.

Examples of difunctional alkyl halides include but are not limited to:1,4-Dibromobutane, 1,5-Dibromopentane, 1,6-Dibromohexane,1,8-Dibromooctane.

Examples of difunctional acid chlorides include but are not limited to:malonyl chloride, isophthaloyl di-acid chloride, sebacoyl chloride,dodecanedioyl dichloride, octanedioic acid dichloride, fumaryl chloride,glutaryl chloride.

Examples of difunctional-anhydrides include but are not limited to:Diethylene-triaminepentaacetic dianhydride,4,4′-(4,4′-Isopropylidenediphenoxy) bis(phthalic anhydride),4,4′-(Hexafluoroisopropylidene)-diphthalic anhydride, bis(phthalicanhydride), 4,4′-Oxydiphthalic anhydride,3,3′,4,4′-Biphenyltetracarboxylic dianhydride,Benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, and Pyromelliticdi-anhydride. Silicones containing two or more anhydride groups perpolymer chain many also be used as cross-linkers. The dual end anhydrideterminated Poly(dimethylsiloxanes) available from Shin Etsu SiliconeCompany and sold under the trade name X-22-2290AS may also be used as across-linking agent.

Examples of Bis-haloalkylether-derivatives include: Bis(chloromethyl)ether, Bis(bromomethyl) ether, bis(iodomethyl) ether, bis(chloroethyl)ether, bis(bromoethyl) ether, bis(iodoethyl) ether.

Activated Esters such as: 3,3′-Dithiodipropionic aciddi(N-hydroxysuccinimide ester) may also be used.

Dual end reactive silicones may also be used as cross-linking agents.Examples of reactive silicones bearing dual end methacrylatefunctionality sold under the trade names X-22-164A; X-22-164B areaavailable from Shin Etsu Silicone company.

Also disclosed herein are methods for making the silicone hydrogelcompositions disclosed herein by actinically-crosslinking theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein (AC-PDMS-PGLY), the method comprising: mixing any ofthe actinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein with an initiator and optionally a hydrophilic monomer(e.g., an ethylenically unsaturated hydrophilic monomer), a hydrophobicmonomer (e.g., an ethylenically unsaturated hydrophobic monomer), anamphiphilic monomer (e.g., an ethylenically unsaturated amphiphilicmonomer), a zwitterionic monomer, an antimicrobial monomer, aUV-blocker, a blue light blocker, a dye, a pigment, a solvent, or acombination thereof, thereby forming a mixture and crosslinking themixture to form a cross-linked silicone hydrogel composition.

Nearly any hydrophilic vinylic monomer can be used. Suitable hydrophilicmonomers comprise, for example, hydroxyl-substituted lower alkyl (C₁ toC₈) (meth)acrylates, (meth)acrylamide, (lower allyl) (meth)acrylamides,ethoxylated (meth)acrylates, hydroxyl-substituted (loweralkyl)(meth)acrylamides, hydroxyl-substituted lower alkyl vinyl ethers,sodium vinyl sulfonate, sodium styrene sulfonate,2-acrylamido-2-methylpropanesulfonic acid, methyl vinyl ether, vinylacetate, and methacrylated glyco-monomers. Examples of hydrophilicmonomers include but are not limited to N-Hydroxyethyl acrylamide;N,N-dimethyl acrylamide (DMA); N-Ethyl acrylamide;N-(3-Methoxypropyl)acrylamide; 2-hydroxyethylmethacrylate (HEMA);2-hydroxyethyl acrylate (HEA); hydroxypropyl acrylate; hydroxypropylmethacrylate (HPMA); N-[Tris(hydroxymethyl)methyl]acrylamide;trimethylammonium 2-hydroxy propylmethacrylate hydrochloride;dimethylaminoethyl methacrylate (DMAEMA); glycerol methacrylate (GMA);N-vinyl-2-pyrrolidone (NVP); dimethylaminoethyl methacrylamide;(meth)acrylamide; allyl alcohol; vinyl pyridine;N-(1,1dimethyl-3-oxobutyl)acrylamide; acrylic acid (AA); methacrylicacid (MAA); N-(2-methacryloyloxy)ethyl-N,N-dimethylammino propanesulfonate; N-(3-methacryloylimino)propyl-N,N-dimethylammino propanesulfonate; N-(3-methacryloylimino)propyl-N,N-dimethylammino propanesulfonate; 2-(methacryloyloxy)ethyl phosphatidylcholine and3-(2′-vinyl-pyridinio) propane sulfonate, 6-O-vinylsebacyl-D-glucose,fructose methacrylate, glucose methacrylate, ribose methacrylate,mannitol methacrylate, sorbitol methacrylate, methacrylatedoligosaccharides, methacrylated oligo-fructose, 2-Acetoacetoxy-ethylMethacrylates, Tetrahydrofurfuryl Methacrylates; 2-HydroxyethylMethacrylates/Succinates; 2-Hydroxyethyl Methacrylate Phosphates;Hepta-O-benzyl monomethacryloyl sucrose. In some examples, the methodscan further comprise forming the hydrophilic monomer. In some examples,copolymers containing vinyl acetate units can be rendered hydrophilicthrough hydrolysis of acetate groups (vinyl alcohol units are formed).For example, poly(vinyl acetate) upon hydrolysis becomes hydrophilic andwater soluble.

Examples of hydrophobic monomers include but are not limited to Methylmethacrylate; ethyl methacrylate; butyl methacrylate; hexylmethacrylate; tert-butyl methacrylate; cyclohexyl methacrylate;Isobornyl Methacrylates; and 2-ethylhexyl methacrylate; heptylmethacrylate; octal methacrylate; Lauryl methacrylate;2,2,2-trifluoroethyl methacrylate, 1,1-dihydroperfluoroethylacrylate,1H,1H,7H-dodecafluoroheptyl acrylate; hexafluoroisopropyl acrylate,1H,1H,2H,2H-heptadecafluorodecyl acrylate, pentafluorostyrene,trifluoromethyl styrene, pentafluoroethyl acrylate, pentafluoroethylmethacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropylmethacrylate (HFIPMA), methacrylate-functionalized fluorinatedpolyethylene oxides; 3-Methacryloxypropyl Tris-(Trimethylsiloxy) Silane,3-Methacryloxypropyl Tris-(Trimethylsiloxy) Silane;Methacryloxyethoxytris-(Trimethylsiloxy) Silane; TrimethylsilylmethylMethacrylate; 1H,1H,11H-Eicosafluoroundecyl Methacrylate; a1H,1H,9H-Hexadecafluorononyl Acrylate; 4-Vinylbenzyl HexafluoroisopropylEther; Pentafluorobenzyl Acrylate; Pentafluorobenzyl Methacrylate;Perfluorocyclohexyl Methyl Acrylate, PerfluorocyclohexylmethylMethacrylate; m-Fluorostyrene and the like.

Examples of Amphiphilic Monomers include but are not limited to2-Methoxyethoxyethyl Methacrylates; Ethoxyethyl Methacrylates;2-(dimethylamino)ethyl methacrylate; 2-(diethylamino)ethyl methacrylate;N-[3-(Dimethylamino)-propyl]acrylamide;N-[3-(Dimethylamino)propyl]meth-acrylamide; Hydroxy oligo(ethyleneglycol)₆ methacrylate; Methoxy oligo(ethylene glycol)₈ methacrylate;N-(1,1-di(O—B-D-glucorpyranosyloxymethyl)-1-(undecyl carbamoyloxymethyl)methyl)acrylamide;5-acrylamido-5-undecylcarbamoyloxymethyl-2,2-dimethyl-cyclol, 3dioxahexane;N-(1,1-(2′,3′,4′6″tetra-O-acetyl-B-D-glucopyranosyloxy-methyl)-1-(undecylcarbamoyloxymethyl)-methyl)-acryl-amide; N-1,1-di(hydroxymethylmethyl)-1(undecylcarbamoyl Oxymethyl)-methyl)acrylamide; N-(1,1-(2, 3, 4,6-″tetra-O-acetyl-ft-D-glucopyranosyloxy-methyl)-1-(undecylcarbamoyloxymethyl)-methyl)-acryl-amide;(2-Hydroxy-3-Methacryloxypropyl) Trimethylammonium Chloride; acrylamidefunctionalized Polyetheramine such as Acrylamide derivatives ofpolyether amines Polyetheramines are available from Huntsman Chemicaland sold under the trade name “Jeffamine” (examples of polyether aminesinclude Jeffamine M-(600, 1000, 2005, 2070)

Zwitterionic Monomers include, but are not limited to,1-(3-Sulfopropyl)-2-Vinylpyridinium Betaine;N-(3-Sulfopropyl)-N-Methacryloxyethyl-N,N-Dimethylammonium Betaine; andN-(3-Sulfopropyl)-N-Methacryloylamidopropyl-N,N-DimethylammoniumBetaine.

Examples of antimicrobial monomers include but are not limited to 2(Methacryloyloxy)-ethyl]-trimethylammonium chloride;2-(methacryloxy)ethyl]dimethyl dodecyl ammonium chloride;2-(methacryloxy)ethyl]-dimethyl hexadecyl ammonium chloride;2-(methacryloxy)decyl]dimethyl hexadecyl ammonium chloride;2-(methacryloxy)-dodecyl]dimethyl hexadecyl ammonium chloride;2-(methacryloxy)hexadecyl]dimethyl hexadecyl ammonium chloride;[2-(methacryloxyethyl]azabicyclo[2.2.2]ammonium chloride;1-{2-[(2-methylprop-2-enoyl)oxy]ethyl}pyridin-1-ium chloride;1-{2-[(2-methylprop-2enoyl)oxy]decyl}pyridin-1-ium chloride;1-{2-[(2-methylprop-2-enoyl)oxy]dodecyl}pyridin-1-ium chloride;1-{2-[(2-methylprop-2-enoyl)oxy]hexadecyl}pyridin-1-ium chloride.

Examples of UV-Blockers include:2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate;2-{2′-Hydroxy-5′-(γ-propoxy)-3′-t-butylphenyl}-5-methoxy-2H-benzotriazole,2-(2H-Benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol; and1-(2-METHYL-ALLYL)-1H-BENZOTRIAZOLE;2-hydroxy-4-Acryloyloxy-benzophenone).

Examples of Blue Light Blockers include various yellow and or orangedyes. Examples of yellow dyes include but are not limited to:N,N-bis-(2-allylcarbomatoethyl)-(4′-phenylazo) aniline,N,N-bis-(2-hydroxyethyl)-(4-phenylazo) aniline;N,N-bis-(2-vinylacetoxyethyl)-(4′-phenylazo)aniline; andN-2-[3‘′-2″-methylphenylazo)-4’-hydroxyphenyl]ethylvinylacetamide.

Examples of orange dyes include but are not limited to: Reactive Orange16 (Reactive Orange 13 (PROCION ORANGE H-2R), disperse orange 3acrylamide, disperse orange 3 meth-acrylamide, disperse orange 3acrylate, disperse orange 3 methacrylate, disperse orange 25 acrylamide,disperse orange 25 methacrylamide, disperse orange 25 acrylate, anddisperse orange 25 methacrylate, Reactive orange dye containing vinylsulfone.

Solvents include, but are not limited to: alcohols such as methanol,ethanol, isopropanol, 1-propanol, n-butanol, tertbutyl alcohol, t-amylalcohol; Isoamyl alcohol; Benzyl alcohol; 2-Ethylhexanolethyleneglycol,propylene glycol; ethyl lactate, cyclopentanone, 2-ethoxyethanol,glycerin, 2-Butoxyethanol; Propylene Glycol Monomethyl Ether; DecylAlcohol; Cyclohexanol; Diethylene glycol monobutyl ether; Glymes such asEthylene glycol dimethyl ether; Ethylene glycol diethyl ether;Diethylene glycol dimethyl ether; Dipropylene glycol dimethyl ether;Diethylene glycol dibutyl ether; Poly(ethylene glycol) dimethyl ether;Tetraethylene glycol dimethyl ether; Ethyl Acetate; Propyl Acetate;n-Butyl Acetate; t-Butyl Acetate; Propylene carbonate; Dimethylcarbonate; Diethyl carbonate; 2 Ethylhexyl Acetate; Butyrolactone;Acetone, methyl ethyl ketone, cyclopentanone; cyclohexanone;2-heptanone, -methyl-2-hexanone; Acetyl acetone; Ethyl propionate;Methyl isobutyl ketone; 2-Butoxyethanol acetate; Bis(2-ethylhexyl)adipate; Methyl phenyl acetate; Methyl lactate; Hexyl acetate; Dimethylform amide, N-methylpyrolidone, 2-Methyl-tetrahydrofuran; N,N-dimethyllactamide, Tetrahydrothiophene (Sulfolane), acetamide, dimethylacetamide. Mixtures of one or more solvents can also be used.

Also disclosed herein are methods of making the UV-Blockingactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein, the methods comprising mixing any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein with a UV-blocker. Also disclosed herein are methods ofmaking UV-blocking silicone hydrogel compositions, the methodscomprising crosslinking any of the UV-Blocking actinically-crosslinkablepolysiloxane-polyglycerol block copolymers described herein.

Also disclosed herein are methods of making the blue light-blockingactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein, the methods comprising mixing any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein with a blue light-blocker. Also disclosed herein aremethods of making blue light-blocking silicone hydrogel compositions,the methods comprising crosslinking any of the blue light-blockingactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein.

Also disclosed herein are methods of making the interpenetrating polymernetworks described herein. The methods of, making the interpenetratingpolymer networks can comprise polymerization any of theactinically-crosslinkable polysiloxane-polyglycerol block copolymersdescribed herein in the presence of a hydrophilic monomer, a hydrophobicmonomer, an amphiphilic monomer, an initiator, a solvent, or acombination thereof. An “interpenetrating polymer network” (IPN) as usedherein refers broadly to an intimate network of two or more polymers atleast one of which is either synthesized and/or crosslinked in thepresence of the other(s). Techniques for preparing IPN are known to oneskilled in the art (see, for example, U.S. Pat. Nos. 4,536,554;4,983,702; 5,087,392; and 5,656,210).

Also disclosed herein are methods of forming a cross-linked network froma polysiloxane-polyglycerol copolymer (PDMS-PGLY) through additionreactions of OH groups (OH from PDMS-PGLY) to suitable bi-functional ordifunctional reagents. This type of reaction is illustrated below.Depending on the ratio of difunctional reagent (X—R—X, X—R—Y) relativeto PDMS-PGLY, a cross-linked network can form or molecular weight mayincrease without resulting in the formation of a cross-linked network.An increase in molecular weight without forming a cross-linked networkis defined as chain extension, which is discussed further below.Gelation is the stage in a chemical reaction at which a polymer is nolonger able to flow due to the formation of a cross-linked network. In atheoretical sense, gelation is characterized by interconnected polymerschains (Network Structure) forming an infinitely large molecule which isnot able to flow. Cross-linking reactions can continue to occur beyondthe point of gelation thereby increasing the degree of rigidity of thepolymer network. Scheme 10 is an illustration showinggelation/Cross-linking/formation of a cross-linked network formationfrom reaction of PDMS-PGLY or AC-(PDMS-PGLY) with X—R—X. Gelation occursif:

$\frac{\left\lbrack {X - R - X} \right\rbrack}{\left\lbrack {{PDMS} - {PGLY}} \right\rbrack} > \propto {{or}\frac{\left\lbrack {X - R - X} \right\rbrack}{\left\lbrack {{AC} - \left( {{PDMS} - {PGLY}} \right)} \right\rbrack}} > \propto$where ∝ is defined as the critical value for gelation to occur.

Chain extension of PDMS-PGLY or AC-(PDMS-PGLY) through reaction withbifunctional agent X—R—X is illustrated in Scheme 11. Chain extensionoccurs if:

$\frac{\left\lbrack {X - R - X} \right\rbrack}{\left\lbrack {{PDMS} - {PGLY}} \right\rbrack} < \propto {{or}\frac{\left\lbrack {X - R - X} \right\rbrack}{\left\lbrack {{AC} - \left( {{PDMS} - {PGLY}} \right)} \right\rbrack}} < \propto$where ∝ is defined as the critical value for gelation to occur.

Chain extension of PDMS-PGLY through reaction with a chain extender isillustrated in Scheme 12.

Use of IPDI as a chain extender to produce AC-CE-(PDMS-PGLY) isillustrated in Scheme 13. Other diisocyanates such as HDI, MDI, etc. canalso be used as chain extending reagents. Scheme 13 illustrates thepreparation of CE-PDMS followed by conversion to AC-CE-PDMS-PGLY.Alternatively, AC-PDMS-PGLY can be formed in step one of a two-stepreaction sequence and then AC-PDMS-PGLY can be converted toAC-CE-PDMS-PGLY in a second step.

Chain extended PDMS-PGLY copolymers described herein are hereby referredto as “CE-PDMS-PGLY”. Copolymers of the present invention can be joinedtogether by mixing PDMS-PGLY with a di-functional monomer (X—R—Y) andoptionally solvent and catalyst to promote addition reactions between OHgroups from polyglycerol segments and the difunctional monomer, andallowing the reaction to proceed until the difunctional-monomer issubstantially consumed. In order to obtain chain extended PDMS-PGLY, theratio of difunctional monomer relative to PDMS-PGLY must be sufficientlylow so as to prevent gelation, as discussed above.

Actinically curable chain extended copolymers described herein arehereby referred to as “AC-CE(PDMS-PGLY)”. These copolymers can be joinedtogether by mixing AC-(PDMS-PGLY) with a di-functional monomer (X—R—Y)and optionally solvent and catalyst to promote addition reactionsbetween OH groups from polyglycerol segments and the difunctionalmonomer, and allowing the reaction to proceed until thedifunctional-monomer is substantially consumed. In order to obtain chainextended AC-(PDMS-PGLY), the ratio of difunctional monomer relative toAC-(PDMS-PGLY) must be sufficiently low so as to prevent gelation, asdiscussed above.

At a sufficiently high ratio of difunctional (X—R—Y) monomer toPDMS-PGLY a cross linked polymer network will form. The “R” group of thedifunctional monomer can comprise alkyl, aryl, and siloxanes of variouslengths. X and Y can be the same or different and can comprise any ofthe following functional groups: epoxy, isocyanate, ester, activatedester, carboxylic acid, Br, Cl, I, anhydride, and acyl-halide. Chainextended block copolymers of polydimethylsiloxane-polyglycerol can befurther converted to actinically curable materials (hereby known asAC-CE-PDMS-PGLY) through reaction with any number of reagents such as2-isocyanatoethylmethacrylate (IEM), methacrylic anhydride, acryloylchloride, 4-vinylbenzyl chloride, or Glycidyl (meth)acrylate.

Examples of difunctional reagents for chain extension include, but arenot limited to, difunctional vinylic compounds, difunctionalisocyanates, difunctional epoxides, difunctional alkyl halides (e.g.,difunctional acid halides), difunctional-anhydrides, bis-halo-alkylderivatives, activated esters, or any number of difunctional reagentscapable for forming chemical bonds with polyglycerol OH groups.

Examples of difunctional reagents known to react with hydroxyl groupsinclude, but are not limited to, divinylethers (J Polym Environ, 2009,17, 123-130).

Examples of difunctional vinyl ether chain extenders include, but arenot limited to: ethylene glycol divinyl ether; 1,-butanedio divinylether; triethyleneglycol divinyl ether; and 1,4-cyclohexane dimethanoldivinyl ether.

Examples of difunctional isocyanate chain extenders include but are notlimited to: Isophorone diisocyanate (IPDI), hexamethylene diisocyanate(HDI), methylene dicyclohexyl diisocyanate, toluene diisocyanate (TDI),Tolylene-2,4-diisocyanate, Tolylene-2,6-diisocyanate,trans-1,4-Cyclohexylene diisocyanate, Poly(propylene glycol), tolylene2,4-diisocyanate terminated, 1,4-Diisocyanatobutane,1,8-Diisocyanatooctane, 1,3-Bis(1-isocyanato-1-methylethyl)benzene,2,2,4-Trimethylhexamethylene Diisocyanate, 2,4,4-TrimethylhexamethyleneDiisocyanate, 1,4-Phenylene diisocyanate, 1,3-Phenylene diisocyanate,m-Xylylene diisocyanate, and methylenediphenyl diisocyanate (MDI).

Examples of difunctional epoxide chain extenders include but are notlimited to: diglycidyl ether, Bisphenol A diglycidyl ether, Glyceroldiglycidyl ether, resorcinol diglycidyl ether, diglycidyl ether,bis(3,4-epoxycyclohexylmethyl) adipate, poly(ethylene glycol) diglycidylether, Bis[4-(glycidyloxy)phenyl]methane, 1,3-Butadiene diepoxide,1,4-Butanediol diglycidyl ether, 1,3-Butanediol diglycidyl ether,Bisphenol F diglycidyl ether, Bisphenol A propoxylate diglycidyl ether,neopentyl glycol diglycidyl ether, N,N-Diglycidyl-4-glycidyloxyaniline,4,4′-Isopropylidenediphenol diglycidyl ether, Poly(propylene glycol)diglycidyl ether, Dicyclopentadiene dioxide, 1,2,5,6-Diepoxycyclooctane,1,2,7,8-Diepoxyoctane, Diglycidyl 1,2-cyclohexanedicarboxylate,3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate,2,5-bis[(2-oxiranylmethoxy)-methyl]-furan (BOF) and2,5-bis[(2-oxiranylmethoxy)methyl]-benzene, Poly(dimethyl siloxane),tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM),tri-glycidyl-aminophenol, e.3-(3-glycidoxypropyl)-1,1,1,3,5,5,5-heptamethyltrisiloxsane,1-epoxyethyl-3,4-epoxycyclohexane, 1,3,5-Triglycidyl isocyanurate,PC-1000 Epoxy Siloxane Monomer (available from Polyset), PC-1035 EpoxySiloxane Monomer (available from Polyset), Poly(dimethylsiloxane),diglycidyl ether terminated (average Mn ˜800, available from SIGMAALDRICH), epoxy terminated Poly(dimethylsiloxanes) available from ShinEtsu Silicone Company and sold under the trade names KF-105; X-22-163A;X-22-163B; X-22-163C; X-22-169AS; X-22-169B available from Shin EtsuSilicone Company; BIS[2-(3,4-EPOXYCYCLOHEXYL)-ETHYLTETRAMETHYLDISILOXANE, and 2,4,6,8-Tetramethyl-2,4,6,8-tetrakis(propylglycidyl ether)cyclotetrasiloxane.

Examples of difunctional alkyl halides include but are not limited to:1,4-Dibromobutane, 1,5-Dibromopentane, 1,6-Dibromohexane,1,8-Dibromooctane.

Examples of difunctional acid chlorides include but are not limited to:malonyl chloride, isophthaloyl di-acid chloride, sebacoyl chloride,dodecanedioyl dichloride, octanedioic acid dichloride, fumaryl chloride,glutaryl chloride.

Examples of difunctional-anhydrides include but are not limited to:Diethylene-triaminepentaacetic dianhydride,4,4′-(4,4′-Isopropylidenediphenoxy) bis(phthalic anhydride),4,4′-(Hexafluoroisopropylidene)-diphthalic anhydride, bis(phthalicanhydride), 4,4′-Oxydiphthalic anhydride,3,3′,4,4′-Biphenyltetracarboxylic dianhydride,Benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, and Pyromelliticdi-anhydride. Silicones containing two or more anhydride groups perpolymer chain many also be used as cross-linkers. The dual end anhydrideterminated Poly(dimethylsiloxanes) available from Shin Etsu SiliconeCompany and sold under the trade name X-22-2290AS may also be used as across-linking agent.

Examples of Bis-haloalkylether derivatives include: Bis(chloromethyl)ether, Bis(bromomethyl) ether, bis(iodomethyl) ether, bis(chloroethyl)ether, bis(bromoethyl) ether, bis(iodoethyl) ether.

Activated Esters such as: 3,3′-Dithiodipropionic aciddi(N-hydroxysuccinimide ester) may also be used.

Dual end reactive silicones may also be used as chain extending agents.Reactive end groups for silicones include, but are not limited to,epoxy, carboxylic anhydride, reactive esters, and alkyl halides.Examples reactive silicones bearing dual end epoxy functionality soldunder the trade names X-22-163; KF-105, X-22-163A; X-22-163B; andX-22-163C available from Shin Etsu Silicone Company. Examples ofreactive silicones bearing dual end carboxylic acid anhydrides include:X-22-168AS, X22-168A, and X-22-168-P5B available from Shin Etsu SiliconeCompany.

Chain extenders (CE) as defined herein are difunctional reactivecompounds (X—R—Y) that are capable of reacting with OH groups (e.g., OHgroups from polyglycerol segments). The R group in the chain extendercan comprise a low molecular weight species or a polymeric species.Chain extenders can be used to join units of PDMS-PGLY or AC-PDMS-PGLYtogether, for example as shown in Scheme 14 and Scheme 15, respectively.PDMS-PGLY-OH+X—R—Y+OH-PGLY-PDMS→PDMS-PGLY—O—R—O-PGLY-PDMSScheme 14. Use of Chain Extender X—R—Y to Join Units of PDMS-PGLYTogether.AC-PDMS-PGLY—OH+X—R—Y+OH-PGLY-PDMS-AC→AC-PDMS-PGLY—O—R—O-PGLY-PDMS-ACScheme 15. Use of Chain Extender X—R—Y to Join Units of AC-PDMS-PGLYTogether.

Reaction of PDMS-PGLY with diisocyanate followed by functionalizationwith methacryloyl chloride to form Chain extended actinicallypolymerizable poly(dimethyl siloxane) bearing polyglycerol branches(AC-CE-PDMS-PGLY) is shown in Scheme 16. Any number of diisocyanates maybe used in the chain extension process. Likewise, any number ofbi-functional vinylic monomers may be used to render the copolymeractinically curable. As previously noted, any number of reagents may beused to chain extend PDMS-PGLY while any number of reagents may be usedto render the copolymer actinically curable.

Also described herein are actinically curable silicone hydrogels(AC-CE-PDMS-PGLY) produced in accordance with the following steps of:(a) mixing PDMS-PGLY with a difunctional monomer (X—R—Y), optionallysolvent and optionally catalyst to promote the formation of chemicallinkages between polyglycerol OH segments, (b) allowing reaction toproceed until difunctional-monomer is substantially consumed, followedby (c) functionalization of CE-PDMS with bi-functional reagents such as(CH2═CR—Z). Some examples of functionalization reagents include:acryloyl chloride, methacryloyl chloride, Glycidyl methacrylate,methacrylic anhydride allyl chloride, vinyl-benzyl chloride, methacrylicacid, acrylic acid, or 2-bromo-methacrylate.

Also described herein are methods of making contact lenses using chainextended or non-chain extended polydimethylsiloxane-polyglycerolcopolymers containing actinically cross-linkable polyglycerol sidebranches described herein, the method comprising the steps of: mixing apolymerization initiator with the AC-PDMS-Polyglycerol and optionallyone or more hydrophilic monomers, one or more hydrophobic monomers, oneor more amphiphilic monomers, one or more zwitterionic monomers; one ormore antimicrobial monomers, one or more UV-blocking monomers, one ormore blue light blocking monomers, and one or more cross-linking agents.Cross-linking reactions can occur through reactions of difunctionalvinylic monomers, difunctional isocyanates, difunctional epoxides,difunctional anhydrides, difunctional alkyl halides, or difunctionalactivated esters.

Also described herein are methods for producing hydrogel membranes withordered structures for use as medical devices or components of medicaldevices. Also disclosed herein are methods of controlling the degree ofordering by addition or removal of various monomers and/or solvents.Furthermore, the degree of ordering can also be altered by increasing ordecreasing temperature.

Also described herein are methods of increasing or decreasing the degreeof self-assembly of the silicone hydrogels formulations described hereinby increasing or decreasing temperature or by adding or removing variousmonomers, or solvent.

In some examples, the methods can further comprise making polyglycerol,such as linear or branched polyglycerol. In some examples, thepolyglycerol can be made via a ring opening polymerization by contactinga reagent suitable for initiating a ring opening polymerization withglycidol. Reagents suitable for initiating ring opening polymerizationsare known in the art and, for example, include, but are not limited to,bases (e.g., alkali metal alkoxides, alkali metal hydroxides, amines).Examples of alkali metal alkoxides include, but are not limited to,NaOCH₃, NaOCH₂CH₃, KOCH₃, KOCH₂CH₃, and KOC(CH₃)₃. Examples of alkalimetal hydroxides, R¹⁴OM where R¹⁴ is H, include NaOH, KOH, LiOH, RbOH,and CsOH.

Branched polyglycerol can be formed through reaction of glycidol withany number of linear, branched or cyclic primary amines or secondaryamines Examples of amino epoxy ring opening polymerization initiatorssuitable for producing polyglycerol include, but are not limited to,NH₃, CH₃(CH₂)_(m)NH₂ where m=0-20, (CH₃)₂CHNH₂, cyclopentyl-NH,cyclohexyl-NH, linear branched or cyclic dialkylamines (e.g.,(CH₃(CH₂)_(m))₂NH where m=1-20, piperidinyl), and trialkyl ammoniumgroups (e.g., (CH₃)₃N, (CH₃CH₂)₃N, (HOCH₂)₃N, (HOCH₂CH₃)₃N). Reagentsother than bases which are nucleophilic may also be used to initiateepoxy ring opening polymerization of glycidol. Thiols and thiol saltsare known to initiate ring opening polymerization of glycidol. Examplesof such thiols include but are not limited to linear, branched or cyclicalkyl-substituted thiol (e.g., HSH, CH₃—SH, CH₃(CH₂)_(m)S, (CH₃)₂CHS,(CH₃)₃CS, cyclohexyl-SH). The molecular weight of branched polyglycerolmay vary from 92 Daltons to 1,11000 Daltons. Molecular weight ofpolyglycerol is determined by the number of repeat units and themolecular weight of the initiating species.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula (III), which can be made using a ring openingpolymerization as shown in Scheme 17, wherein R¹⁴OM is an alkali metalalkoxide or alkali metal hydroxide reagent suitable for initiating thering opening polymerization. R¹⁴ can comprise, for example, H, alkyl, orcycloalkyl, either of which is optionally substituted with halide,hydroxy, thioether, carbonyl, alkoxy, alkylhydroxy, carboxyl, amido,alkyl, alkenyl, alkynyl, aryl, —C(O)NR^(x)R^(y), or a combinationthereof, and R^(x) and R^(y) are independently H, OH, alkyl, alkenyl,alkynyl, cycloalkyl, aryl, alkylaryl, or heteroaryl. In some examples,R¹⁴ can comprise H, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,or tert-butyl. M comprises an alkali metal, e.g., Li, Na, K, Rb, or Cs.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula (IV), which can be made using a ring openingpolymerization as shown in Scheme 18.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula (V), which can be made using a ring openingpolymerization as shown in Scheme 19, where R¹⁵ and R¹⁶ are,independently, H, alkyl, or cycloalkyl, either of which is optionallysubstituted with halide, hydroxy, thioether, carbonyl, alkoxy,alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,—C(O)NR^(x)R^(y), or a combination thereof; or R¹⁵ and R¹⁶, togetherwith the atoms to which they are attached, form a 3-10 membered cyclicmoiety, wherein any of the additional atoms are optionally heteroatomsand the 3-10 membered cyclic moiety is optionally substituted withhalide, hydroxy, thiol, carbonyl, alkoxy, alkylhydroxy, carboxyl, amido,alkyl, alkenyl, alkynyl, aryl, —C(O)NR^(x)R^(y), or a combinationthereof; and R^(x) and R^(y) are independently H, OH, alkyl, alkenyl,alkynyl, cycloalkyl, aryl, alkylaryl, or heteroaryl. In some examples,R¹⁵ and R¹⁶ are, independently, H, CH₃, CH₃CH₂, CH₃(CH₂)_(n) wheren=1-20, cyclopentyl, cyclohexyl, piperidinyl, (CH₃)₃, (CH₃CH₂)₃,(HOCH₂)₃, or (HOCH₂CH₃)₃.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula (VI), which can be made using a ring openingpolymerization as shown in Scheme 20.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula (VII), which can be made using a ring openingpolymerization as shown in Scheme 21.

In some examples, the polyglycerol can comprise a branched polyglyceroldefined by Formula (VIII), which can be made using a ring openingpolymerization as shown in Scheme 22.

The present invention is not to be limited in scope by the specificembodiments described which are intended as single illustrations ofindividual aspects of the invention, and functionally equivalent methodsand components are within the scope of the invention. Indeed, variousmodifications of the invention, in addition to those shown and describedherein, will become apparent to those skilled in the art from theforegoing description and accompanying drawings using no more thanroutine experimentation. Such modifications and equivalents are intendedto fall within the scope of the appended claims.

The examples below are intended to further illustrate certain aspects ofthe compositions and methods described herein and are not intended tolimit the scope of the claims.

EXAMPLES

The following examples are set forth below to illustrate the methods andresults according to the disclosed subject matter. These examples arenot intended to be inclusive of all aspects of the subject matterdisclosed herein, but rather to illustrate representative methods,compositions, and results. These examples are not intended to excludeequivalents and variations of the present invention, which are apparentto one skilled in the art.

Efforts have been made to ensure accuracy with respect to numbers (e.g.,amounts, temperature, etc.) but some errors and deviations should beaccounted for. Unless indicated otherwise, parts are parts by weight,temperature is in ° C. or is at ambient temperature, and pressure is ator near atmospheric. There are numerous variations and combinations ofreaction conditions, e.g., component concentrations, temperatures,pressures, and other reaction ranges and conditions that can be used tooptimize the product purity and yield obtained from the describedprocess. Only reasonable and routine experimentation will be required tooptimize such process conditions.

Polydimethylsiloxane bearing polyglycerol branches (PDMS-PGLY) can besynthesized as illustrated in Scheme 9. Alternatively, PDMS-PGLY isavailable from Shin Etsu Chemical Co., Ltd and sold under the tradenames of KF6100 (viscosity ˜40,000 mPa*sec) and KF6104 (viscosity ˜4,000mPa*sec).

2-Hydroxy-2-methylpropiophenone (Daracure 1173),2-Hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959),Dibutyltin dilaurate (DBTDL), 2-Isocyanatoethyl methacrylate (IEM),Isophorone diisocyanate (IPDI), diethylene glycol, were obtained fromSIGMA-ALDRICH. NVP was obtained from Shijiazhuang Aopharm Import &Export Trading Co., Ltd. Glyceryl monomethacrylate (GMMA) Methyldi(trimethylsiloxy) silylpropylglyceryl methacrylate (SIGMA) and wasobtained from Bimax Chemicals Ltd.

Larger or smaller batch sizes as described herein can be employed toproduce AC-(PDMS-PGLY), AC-CE-(PDMS-PGLY), or CE-(PDMS-PGLY). A solventcan be used in the synthesis operations to improve mixing, reduceviscosity, and/or improve control of reaction temperature. Equipmentspecifically designed for the mixing of viscous materials can be used asa means of improving mixing and control of reaction temperature.Increasing the ratio of diisocyanate relative to PDMS-PGLY (KF6100) canresult in an increase in molecular weight while increasing the ratio ofIEM relative to PDMS-PGLY and or diisocyanate can yield copolymerscapable of forming more highly cross-linked networks.

Measurement of Contact Lens Water Content

The refractive index of a hydrogel is dependent on water content of thematerial. The water content of contact lenses described herein weremeasured based on this principle using an ATAGO handheld refractometer.ATAGO corporation sells handheld refractometers that are calibrated in %Solids (BRIX) or % Water depending on the model. If one uses a handheldrefractometer calibrated in BRIX, then the water content of the contactlens=100−BRIX reading.

Measurement of Oxygen Permeability (Dk)

Oxygen permeability was determined using a polarographic measurementmethod. Rheders 02 Measurements were performed using Permeometer model201T. Details for measuring oxygen permeability are available in ANSIZ80.20-2010.

Methods of Manufacturing Contact Lenses

Lathe cut contact lenses can be produced by using a lathe (example, useof ophthalmic lathe manufactured Sterling Ultra Precision Optiform 40,Optiform 60 or Optiform 80) to shape one surface of a singled sidedmolded part or by lathe shaping both the front and back surface of acontact lens material. Cured contact lens material in the form ofblanks, bonnets, disks or buttons can be produced in plastic molds,glass molds, or metal molds. Alternatively, contact lens disks can beformed by filing a cylindrical tube with contact lens fluid material,curing the material, removing the resulting rod, cutting the rod intodisks and forming a contact lens by double sided lathing (DSL). If thecontact lens formulation is cured in a mold that imparts an opticalquality anterior or posterior surface, only one side the resultingbonnet (blank) requires lathe cutting. For example, a contact lens canbe produced by filling a bonnet shaped mold with a lens-forming fluidmaterial, curing the lens formulation in the bonnet shaped mold, whereinthe bonnet shaped mold includes a molding surface with optical quality,wherein the molding surface defines one of the posterior and anteriorsurface of the contact lens. Then the bonnet is removed from the moldand the anterior or posterior surface is formed by direct lathing of thebonnet on the side opposite to the molded surface (methods of producinglathe cut contact lenses are described in U.S. Pat. Nos. 3,835,588;4,924,739; 5,347,896; and 7,213,918).

Contact lenses can be manufactured by a process known as double sidedmolding (DSM). This method comprises the steps of providing a mold formaking a soft contact lens, wherein the mold has a one mold half withmolding surface defining the anterior surface of a contact lens and asecond mold half with a second molding surface defining the posteriorsurface of the contact lens. Typically, in the DSM process, a liquidcontact lens formulation is dispensed into the female mold half, themale mold half is affixed to the female mold half and the fluid isconverted to a solid in a polymerization reaction. Polymerization andcross-linking reactions (curing) are typically triggered by applyingthermal energy or actinic radiation (e.g., visible light, UVA, UVB, UVC)thereby converting the liquid formulation into a solid contact lens.Contact lens formulations cured with actinic radiation can contain aphoto-initiator suitable for use with the radiation source. For example,if one desires to cure contact lens formulation with visible light, thelens formulation can contain a visible light photo-initiator. If onedesires to cure a contact lens formulation using UV radiation, the lensformulation can contain a UV photo-initiator. If one desires to cure acontact lens formulation using thermal energy, the formulation cancontain a thermal initiator.

In a process known as double sided molding, contact lenses may be formedby molding the front surface and back surface of the lens. Materialsused to make contact lens molds may be suitable for single use orrepeated use. Double sided molding technology used in the production ofcontact lenses is described in a number of patents (e.g., U.S. Pat. Nos.4,209,289; 4,347,198; 4,121,896; 5,271,874; 5,776,381; 8,491,824;EP0802852A2; U.S. Pat. No. 6,113,817). Contact lens molds are typicallymade from polypropylene or polystyrene. However, the mold can be madefrom any number of other materials including: nylon, glass, quartzglass, and metal. Single use contact lens molds are generally made frominexpensive plastics such as polypropylene, polystyrene, and polymethylmethacrylate. The contact lens mold materials should be chemicallycompatible (non-damaging) with the contact lens formulations. Re-usablemolds can be made from glass/quartz, metals (e.g., stainless steel,tungsten carbide, titanium alloys, cobalt alloys, nickel alloys, copperalloys), ceramic materials, or suitable engineering resins. Engineeringresins include but are not limited to composite materials which cancontain glass fibers (“fiber glass”), carbon fibers, or boron fibers,Common engineering resins include materials such as polycarbonate,polyetheretherketone, polyetherimide (PEI), Topas (cyclic-olefinpolymer, COC resin), nylon (Nylon 6; Nylon 12; Nylon 6,6; glass filledNylons), polyphenylenesulfide, glass filled epoxy resin,polyphenyleneoxides (Noryl), polyesters (polybutylene terephthalate,Delrin (DuPont), glass filled polyesters (glass filled unsaturatedpolyester resins), polycarbonate-acrylic alloy, polyamide-imide,polyether sulphone, polytetrafluoroethylene and perfluoroalkylvinylether copolymer, polyvinylidene fluoride, perfluoroalkoxy alkane, andtetrafluoroethylene hexafluoropropylene vinylidene copolymer.

Contact lenses described herein were prepared in polypropylene contactlens molds using spin cast manufacturing technology. Spin castmanufacturing of contact lenses is described in a number of patents(e.g., U.S. Pat. Nos. 3,660,545; 3,408,429; 3,699,089; 4,517,139;4,590,018). In spin cast manufacturing of contact lenses, molds aredosed with a formulation and rotated at a defined speed (in the absenceof externally applied UV light) and then polymerization is triggered byUV light, thermal energy, or both. The centrifugal forces resulting fromrotational motion helps spread (wet) the contact lens formulation acrossthe mold and provides the concave lens curvature. Wetting of the contactlens molds by the lens formulation can be facilitated by surfacetreatment of the molds (e.g., corona or plasma treatment) and/orspinning at high speed (often at a speed higher than that which is usedto obtain a specific lens power). Once molds containing the contact lensformulation are sufficiently wetted, the rotational speed is adjusted toachieve a targeted lens power. In the case of high speed spinning(higher than that desired for a particular lens power), rotational speedis decreased and the liquid monomer moves inward and a receding contactangle will be present at the lens edge. UV irradiation of the lensformulation triggers polymerization of the liquid lens monomer andprovides a solid lens having a smooth edge. The resulting lens ischaracterized by a convex optical surface which corresponds to theconcave surface of the mold and a concave optical surface whose geometryhas been created, mainly by the centrifugal force. Polymerization of thelens formulation is typically conducted in a low oxygen environment. Alow oxygen environment can be achieved by displacing air in a curechamber with a gas such as nitrogen, argon, CO₂, or any number of gasesthat do not interfere with free radical polymerization.

Procedure for Preparation of Contact Lenses

The contact lenses can be produced using variety methods known in theart, such as double sided molding (DSM), spin casting, single sidedmolding single with single sided lathing (SSM-SSL), and double sidedlathing (DSL).

Contact lenses described herein were prepared using spin casttechnology. Briefly, about 14 to 20 microliters of lens formulation wasdosed into corona treated polypropylene molds (the amount of contactlens formulation dosed into the molds varied depending on targetedoptical power and thickness profile). The molds containing the contactlens formulation were rotated in the absence of externally applied UVlight at a speed above that used during the polymerization process toaid in the wetting of the molds and spreading the contact lensformulation. Rotational speed of the molds containing lens formulationwas then decreased sufficiently to achieve a targeted lens power. Aftera defined amount of time in a nitrogen flushed chamber, polymerization(cure) was triggered by irradiating the spinning molds containing thelens formulation with UV light. The spinning molds containing thecontact lens formulation were irradiated from about 5 minutes to 45minutes with UVA radiation (Intensity was from about 3 mW/cm² to 6mW/cm²) while nitrogen was continuously flushed through the curingchamber. The time needed for sufficient polymerization/cure depends, inpart, on UV intensity, initiator concentration, volume of contact lensformulation, and the concentration of oxygen in the lens formulation andcuring chamber. Although the contact lenses herein were UV cured in anitrogen atmosphere, other types of atmospheres can be used. The curingof the contact lenses can be conducted under nitrogen, argon, CO₂, or inair atmospheres. Since oxygen is known to interfere with free radicalpolymerization of contact lens formulations, curing/polymerization isideally conducted in an atmosphere with a low percentage of oxygen. Ifone desires to cure the lens formulations described herein in air,photo-initiator concentration can be increased to overcomepolymerization inhibition and retardation caused by oxygen. If desired,cured or partially cured contact lenses can be subjected to post curingusing thermal energy in order to minimize residual monomer content.Inclusion of both a UV and thermal polymerization initiator(s) in acontact lens formulation is preferable for processes that involveinitial cure by UV light followed by thermal post cure. Contact lensformulation can also be cured in a heated UV chamber.

BSA Protocol

For the BSA assay, 0.1 mL of each standard and unknown sample replicatewere pipetted into an appropriate labeled test tube. Next, 2.0 mL of theworking reagent (WR) was added to each tube and the mixture was mixedwell (sample to WR ratio=1:20). The tubes are then covered and incubatedat a selected temperature for a selected time.

For a standard protocol, the tubes were incubated at 37° C. for 30minutes (working range=20-2,000 μg/mL). For a room temperature (RT)protocol, the tubes were incubated at room temperature for 2 hours(working range=20-2,000 μg/mL). For an enhanced protocol, the tubes wereincubated at 60° C. for 30 minutes (working range=5-250 μg/mL).Increasing the incubation time or temperature increases the net 562 nmabsorbance for each test and decreases both the minimum detection levelof the reagent and the working range of the protocol. A water bath isused to heat the tubes for either the Standard (37° C. incubation) orEnhanced (60° C. incubation) Protocol. Using a forced-air incubator canintroduce significant error in color development because of uneven heattransfer.

Following incubation at the selected temperature for the selected time,all tubes were cooled to room temperature. With the spectrophotometerset to 562 nm, the instrument was zeroed on a cuvette filled only withwater. Subsequently, the absorbance for all samples was measured within10 minutes. Because the BSA assay does not reach a true end point, colordevelopment will continue even after cooling to room temperature.However, because the rate of color development is low at roomtemperature, no significant error will be introduced if the 562 nmabsorbance measurements of all tubes are made within 10 minutes of eachother. The average 562 nm absorbance of the blank standard replicates issubtracted from the 562 nm absorbance measurement of all otherindividual standard and unknown sample replicates. A standard curve isprepared by plotting the average blank-corrected 562 nm measurement foreach BSA standard vs. its concentration in μg/mL. The standard curve canthen be used to determine the protein concentration of each unknownsample.

Preparation of Actinically Curable Copolymers Comprised of aPolydimethylsiloxane Main Chain with Polyglycerol Branches(AC-(PDMS-PGLY)) Bearing an Ethylenically Unsaturated Functionality(Examples 1-7) Example 1 (1002-138-1), Macromer-1

AC-PDMS-PGLY: An actinically curable copolymer comprised of apolydimethylsiloxane main chain with polyglycerol branches bearingethylenically unsaturated functionality (AC-PDMS-PGLY) was prepared asfollows: A reaction vessel was charged with of KF6100 (40.94 grams), IEM(1.283 grams), and DBTDL (0.046). The components were mixed untilhomogenous and the reaction was allowed to proceed at 35-40° C. untilthe isocyanate group (NCO) from IEM was no longer visible by FT-IR.

Example 2 (1002-138-2), Macromer-2

An actinically curable copolymer comprised of a polydimethylsiloxanemain chain with polyglycerol branches bearing ethylenically unsaturatedfunctionality (AC-PDMS-PGLY) was prepared as follows: KF61004 (40.10grams), methacrylic anhydride (2.55 grams), Aberlyst 15 (0.48 grams) andethyl acetate (100 mL). The components were mixed until homogenous andthe reaction was allowed to proceed at 35-40° C.

Example 3 (1002-138-3), Macromer-3

An actinically curable copolymer comprised of a polydimethylsiloxanemain chain with polyglycerol branches bearing ethylenically unsaturatedfunctionality (AC-PDMS-PGLY) was prepared as follows: A reaction vesselwas charged with KF6104 (40.44 grams), IEM (1.29 grams) and DBTDL (0.05grams). The components were mixed until homogenous and the reaction wasallowed to proceed at 35-40° C. until the NCO group from IEM was nolonger visible by FT-IR.

Example 4 (1002-152-1), Macromer-4

An actinically curable copolymer comprised of a polydimethylsiloxanemain chain with polyglycerol branches bearing ethylenically unsaturatedfunctionality (AC-PDMS-PGLY) was prepared as follows: A reaction vesselwas charged with KF6100 (40.69 grams), IEM (0.65 grams) and DBTDL (0.029grams). The components were mixed until homogenous and the reaction wasallowed to proceed at 35-40° C. until the NCO group from IEM was nolonger visible by FT-IR.

Example 5 (1002-152-2), Macromer-5

An actinically curable copolymer comprised of a polydimethylsiloxanemain chain with polyglycerol branches bearing ethylenically unsaturatedfunctionality (AC-PDMS-PGLY) was prepared as follows: A reaction vesselwas charged with KF6104 (42.30 grams), IEM (0.64 grams) and DBTDL (0.033grams). The components were mixed until homogenous and the reaction wasallowed to proceed at 35-40° C. until the NCO group from IEM was nolonger visible by FT-IR.

Example 6 (1002-152-3), Macromer-6

An actinically curable copolymer comprised of a polydimethylsiloxanemain chain with polyglycerol branches bearing ethylenically unsaturatedfunctionality (AC-PDMS-PGLY) was prepared as follows: A reaction vesselwas charged with KF6104 (30.23 grams), IEM (1.48 grams) and DBTDL (0.025grams). The components were mixed until homogenous and the reaction wasallowed to proceed at 35-40° C. until the NCO group from IEM was nolonger visible by FT-IR.

Example 7 (1002-152-7), Macromer-7

A reaction vessel was charged with 23.54 grams of Polyglycerol branchedPolydimethylsiloxane (KF6100), 1.446 grams of IEM and 0.036 grams ofDBTDL. The components were mixed until homogenous and the reaction wasallowed to proceed at 35-40° C. until the isocyanate group from IEM wasno longer visible by FT-IR.

Chain Extension and/or Cross-Linking of PDMS-PGLY Using IsophoroneDiisocyanate (Example 8-13) Example 8 AC-CE-(PDMS-PGLY) (1002-156-1),Macromer-8

A reaction vessel was charged with KF6100 (18.80 grams), IPDI (1.20grams, 5.398 mmol) and DBTDL (0.04 grams). The contents of the reactionvessel were mixed until homogenous and then heated at 35-40° C. untilNCO functionality was no longer visible by FT-IR. The resultingcopolymer was noticeably more viscous, but it remained fluid. IEM (0.65grams) was then added to the reaction vessel allowed react until all NCOfrom the IEM was no longer visible by FT-IR. This example demonstratesunder the conditions of 0.287 mmol diisocyanate (IPDI) per gram ofKF6100 chain extension may be accomplished without causing gelation(i.e.; cross-linked network).

Example 9 CE-(PDMS-PGLY) (1002-154-4)

A plastic centrifuge tube was charged with KF6100 (5.30 grams) IPDI(0.51 grams, 2.29 mmol) and DBTDL (0.5 mg). The resulting fluid wasmixed and allowed to react for 12 hours at room temperature. Afterheating for several hours at 70° C., the sample remained fluid. Thisexample demonstrates that KF6100 may be chain extended under theconditions of 0.97 mmol IPDI per gram of KF6100.

Example 10 [CE-(PDMS-PGLY)] (1002-154-5)

A plastic centrifuge tube was charged with KF6100 (5.01 grams) IPDI(1.08 grams, 4.86 mmol), diethylene glycol (1.10 grams) and DBTDL (3drops). Upon mixing the resulting solution became warm to the touch andits viscosity increased. After the solution was no longer warm to thetouch, it was spread over a 6 inch×4 inch sheet of polyethylene whichwas then placed in an oven preheated to 70° C. After 30 minutes at 70°C., the sample remained fluid. Isophorone diisocyanate (IPDI) used inthis experiment was doped with 0.1 mg of DBTDL per mL.

Example 11 [CE-(PDMS-PGLY)] (1002-154-6)

A plastic centrifuge tube was charged with KF6100 (5.35 grams) IPDI(21.54 grams, 96.9 mmol), and diethylene glycol (2.01 grams). Uponmixing the resulting solution became warm to the touch and viscosityincreased noticeably. After the solution was no longer warm to thetouch, it was spread over a 6 inch×4 inch sheet of polyethylene whichwas then placed in an oven preheated to 70° C. After curing for 30minutes at 70° C., the sample remained fluid (not cross-linked).Isophorone diisocyanate (IPDI) used in this experiment was doped with0.1 mg of DBTDL per mL.

Example 12 [CE-(PDMS-PGLY)]

A plastic centrifuge tube was charged with KF6104 (2.56 grams) IPDI(1.96 grams, 8.82 mol), 1.93 grams of diethylene glycol and 3 drops ofDBTDL. Upon mixing the resulting solution became warm to the touch andviscosity increased noticeably. After the solution was no longer warm tothe touch, it was spread over a 6 inch×4 inch sheet of polyethylenewhich was then placed in an oven preheated to 70° C. oven for 30minutes, removed and examined. It was noted that the sample remainedfluid.

Example 13 (1002-154-8)

A blend comprising two different PDMS-PGLY copolymers was prepared. Aplastic centrifuge tube was charged with KF6100 (25.03 parts by weight)and KF6104 (14.24 parts by weight). Components were mixed to yield acloudy solution. No further experimentation was performed with thissample.

Evaluation of Formulations Containing Modified PDMS-PGLY (Examples14-23) Example 14 (1002-138-F-01)

A formulation containing copolymer prepared in example 1 (1.024 gramsof) was combined with DARACURE 1173 (0.016 grams), of isopropanol (0.501grams) and mixed until homogenous. 0.25 grams of the formulation wasplaced in a polyethylene plastic mold (diameter ˜30 mm) and then exposedto UVA (˜3 mW/cm²) for 10 minutes after which a clear tacky gel wasobtained.

Example 15 (1002-138-F-02)

Formulation prepared in Example 11 (˜0.75 grams) was combined with GMMA(˜0.25 grams). Approximately 0.25 grams of the formulation was placed ina polyethylene plastic cap (diameter ˜30 mm) and then exposed to UVA (˜3mW/cm²) for 10 minutes after which a clear gel was obtained.

Example 16 (1002-138-F-03)

A formulation containing 7.5 grams sample prepared in example 1 wascombined with NVP (3.675 grams), SIGMA (3.675 grams), AMA (0.075 grams),and Daracure 1173 (0.078 grams) and mixed until homogenous. Theformulation was subjected to a UV cure test and mechanical performancetesting as follows: a portion of the formulation was spread in a plasticcap (diameter ˜30 mm) and then exposed to UVA light (˜3 mW/cm²) for 15minutes after which a clear gel was obtained. The gel was allowed tohydrate in water for 20 minutes after which a clear hydrogel wasobtained. The elastic properties of the gel were evaluated by grippingthe hydrated sample between forefinger and thumb and then gentlystretching it until it broke. The gel evaluated in this example wasstretched to −50-75% of its original length before breaking.

Example 17 (1002-138-3-F-01)

A formulation containing 1.024 grams copolymer from Example 3 wascombined with, and 0.016 grams Daracure 1173 (0.05 grams) andisopropanol (0.38 grams). After mixing a slightly cloudy fluid wasobtained. A portion of the formulation was spread in a plastic cap (˜30mm diameter) and then exposed to UVA light (˜3 mW/cm2) for 10 minutes toyield a tacky material.

Example 18 (1002-138-1-F02)

A formulation containing 0.75 grams of formulation from Example 13 wascombined with, GMMA (0.25 grams), Daracure 1173 (0.05 gram) andisopropanol 0.38 grams) and mixed. formulation was spread in plastic capand irradiated with UVA (about 3 mW/cm2) for about 10 minutes to yield agel.

Example 19 (1002-138-1-F03)

A formulation was prepared by combining 7.516 grams of macromer(prepared as described in example 1) with SIGMA (3.726 grams), GMMA(3.717 grams) and Daracure 1173 (0.062 grams).

Example 20 (1002-138-1-F04)

A formulation was prepared by combining about a 15 grams of formulationfrom Example 16 (1002-138-1-F03) with AMA (0.005 grams), IPA (21 grams),and Daracure 1173 (0.005 grams). About 3 mL of the mixture was placed ina plastic beaker and exposed with UVA (about 3.5 mW/cm2) for about 30minutes. The formulation remained fluid and did not form a gel.

Example 21 (1002-138-1-F05)

A formulation was prepared by combining 7.601 grams of copolymer(prepared as described in example 1) with 3.705 grams of NVP, 3.774grams of SIGMA, and 0.077 grams of allyl methacrylate (AMA). Aftermixing a clear solution was obtained. A plastic mold (˜30 mm diameter)was dosed with formulation and then placed under UVA (3.5 mW/cm2) for 15minutes to yield a clear gel. The gel was extracted in 5 mL ofisopropanol for 15 minutes and then soaked in 10 mL of purified water.The resulting gel was clear, lubricous and displayed good elasticity.The gel could be stretched to 100% its original length before breaking.

Example 22 (1002-154-1)

A formulation was prepared by combining 3.63 grams of copolymer(prepared as described in example 1) with 2.50 grams of isopropanol. 1gram of sample was placed in a plastic mold (˜30 mm) and then exposed toUVA (˜3.5 mW/cm2) for ˜20 minutes. The sample did not gel under theseconditions.

Example 23 (1002-154-2)

A formulation was prepared by combining 3.54 copolymer prepared inexample 7 with 1.51 grams IPA solution containing 3.33 mg/mL of IRGACURE2951. The resulting formulation was spread on polyethylene sheet to givea sample thickness of −0.2 cm. The sample was exposed to UVA (˜3.5mW/cm²) for 30 minutes to yield a gel. The resulting gel was hydrated inwater to yield a lubricous silicone hydrogel film.

Formulation of Cross-Linked Network fromPolydimethylsiloxane-Co-Polyglycerol (KF6104) and Diisocyanate (IPDI)(Example 24-25) Example 24 (1002-153-1)

A formulation was prepared by combining 5.142 grams of KF6104, 0.186grams of IPDI, and 0.022 grams DBTDL, as shown in Table 5. Theformulation was mixed for 30 seconds and then poured into circular molds(diameter ˜30 mm) and sonicated for 2 minutes and allowed to cure atroom temperature for 10 minutes. After 15 minutes at room temperature,the samples were placed in an oven pre-heated to 70° C. to yield cleargels (cross-linked).

Example 25 (1002-153-2)

A formulation was prepared by combining 5.303 grams of KF6104, 0.396grams of IPDI, and 0.04 grams DBTDL, as shown in Table 5. Theformulation was mixed for 30 seconds and then poured into circular molds(diameter ˜30 mm) and sonicated for 2 minutes and allowed to cure atroom temperature for 10 minutes. After 15 minutes at room temperature,the samples were placed in an oven pre-heated to 70° C. to yield clear(cross-linked) gels.

TABLE 5 Cross-linking of PDMS-Polyglycerol with Diisocyanate(isophoronediisocyanate) Example 24 (1002-153-1) Example 25 (1002-153-2)Grams/ Percent by Grams/ Percent by Macromers Parts Weight Parts WeightKF6104 5.142 96.11 5.303 92.40 IPDI 0.186 3.48 0.396 6.90 DBTDL 0.0220.41 0.04 0.70 Total 5.35 100.0 5.739 100.0 Comment Formed Clear GelFormed Clear Gel

Preparation of Modified PDMS-Polyglycerol Formulations Example 26AC-CE-(PDMS-PGLY) (1002-156-1), Macromer-26

A reaction vessel was charged with branched 18.8 grams of PDMS-PGLY(KF6100, Viscosity ˜40,000 cps), 1.20 grams of IPDI and 2 drops (0.02grams) of DBTDL. The components were mixed until homogenous and thereaction was allowed to proceed at 35-40° C. until the isocyanate group(NCO) from IPDI was no longer visible by FT-IR. The viscosity of themixture was noticeably higher after reaction with IPDI. The resultingcopolymer was then allowed to react with IEM (0.65 grams) at 35-40° C.until the isocyanate group from IEM was no longer visible by FT-IR. Thiscopolymer (Macromer-26) was used to prepare additional formulations andcontact lenses therefrom (described below).

Example 27 (PDMS-PGLY-01)

A formulation (PDMS-PGLY-01) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to procedure described in Example 26), glycerolmethacrylate (GMMA), and Daracure 1173 (photoinitiator) as shown inTable 6. Before curing, the formulation was clear. Contact lenses werethen prepared from the formulation. Contact lenses were then preparedfrom the formulation using spin cast technology with UV curing, asdescribed further below. The prepared contact lenses exhibited phaseseparation and a cloudy ring, and had a clarity rank of 7. The preparedcontact lenses had an average diameter of 13.8 mm.

Example 28 (PDMS-PGLY-02)

A formulation (PDMS-PGLY-02) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to procedure described in Example 26), GMMA,2-hydroxyethylmethacrylate (HEMA), and Daracure 1173 as shown in Table6. Before curing, the formulation was clear. Contact lenses were thenprepared from the formulation using spin cast technology with UV cure ina nitrogen flushed UV light chamber, as described above. The preparedcontact lenses exhibited phase separation and had a clarity rank of 7.The prepared contact lenses had an average diameter of 14 mm.

Example 29 (PDMS-PGLY-03)

A formulation (PDMS-PGLY-03) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to procedure described in Example 26), GMMA, HEMA,and Daracure 1173 as shown in Table 6. Before curing, the formulationwas clear. Contact lenses were then prepared from the formulation usingspin cast technology with UV cure in a nitrogen flushed UV lightchamber, as described above. The prepared contact lenses exhibited phaseseparation and had a clarity rank of 7. The prepared contact lens had anaverage diameter of 14 mm.

Example 30 (PDMS-PGLY-04)

A formulation (PDMS-PGLY-04) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to procedure described in Example 26), GMMA, HEMA,Daracure 1173, and water as shown in Table 6. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contactlenses exhibited phase separation and had a clarity rank of 6. Theprepared contact lenses had an average diameter of 14.1 mm. The preparedcontact lenses had an oxygen permeability (D_(k)) of 66.

Example 31 (PDMS-PGLY-05)

A formulation (PDMS-PGLY-05) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to procedure described in Example 26), GMMA, HEMA,and Daracure 1173 as shown in Table 6. Before curing, the formulationwas clear. Contact lenses were then prepared from the formulation usingspin cast technology with UV cure in a nitrogen flushed UV lightchamber, as described above. The prepared contact lens exhibited phaseseparation and had a clarity rank of 5. The prepared contact lenses hadan average diameter of 15.8 mm. The prepared contact lenses had anoxygen permeability (D_(k)) of 66.

TABLE 6 Formulations containing modified PDMS-Polyglycerol. ExampleExample Example Example Example 27 28 29 30 31 (PDMS- (PDMS- (PDMS-(PDMS- (PDMS- PGLY-01) PGLY-02) PGLY-03) PGLY-04) PGLY-05) MaterialsPercent Percent Percent Percent Percent AC-CE- 49.25 49.25 39.42 35.4919.70 (PDMS- PGLY)* GMMA 49.25 36.94 44.34 39.92 59.11 HEMA 0.00 12.3114.78 13.30 19.70 Initiator 1.50 1.50 1.47 1.32 1.48 (Daracure 1173)water 0.00 0.00 0.00 9.97 0.00 Total 100 100 100 100 100 Formulationclear clear clear clear clear Before Cure Lens Phase Phase Phase PhasePhase Appearance separation separation separation separation separationCloudy ring Lens Clarity 7 7 7 6 5 Rank Lens ~13.8 ~14.0 14 14.0-14.2015.8 Diameter (mm) Average 13.8 14 14 14.1 15.8 Diameter (mm) Dk — — —66 110 *AC-CE-(PDMS-PGLY) was prepared according to procedure describedin Example 26; Lens Clarity Rank is from 1 to 10, with 1 being the worst(completely opaque); Dk = Oxygen permeability of a contact lens isabbreviated, where “D” is diffusivity (cm²/sec) and “k” is thesolubility of oxygen in a given contact lens material (ml O²/ml ofmaterial × mm Hg); Contact lenses were prepared by UV curing in anitrogen flushed chamber using spin cast technology as described above.

Example 32 (PDMS-PGLY-06)

A contact lens formulation (PDMS-PGLY-06) was prepared by combiningAC-CE-(PDMS-PGLY) (prepared according to the procedure described inExample 26), GMMA, N-vinyl-2-pyrrolidone (NVP), and Daracure 1173 asshown in Table 7. Before curing, the formulation was clear. Contactlenses were then prepared from the formulation using spin casttechnology with UV cure in a nitrogen flushed UV light chamber, asdescribed above. The prepared contact lenses had a diameter of −15 mm.

Example 33 (PDMS-PGLY-07)

A formulation (PDMS-PGLY-07) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), GMMA,NVP, Daracure 1173, and water as shown in Table 7. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lensexhibited phase separation and had a clarity rank of 8. The preparedcontact lenses had an average diameter of 14.1 mm.

Example 34 (PDMS-PGLY-08)

A formulation (PDMS-PGLY-08) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), GMMA,NVP, Daracure 1173, and water as shown in Table 7. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lensexhibited phase separation and had a clarity rank of 6. The preparedcontact lenses had an average diameter of 14.1 mm. The prepared contactlenses had an oxygen permeability (D_(k)) of 64.

Example 35 (PDMS-PGLY-09)

A formulation (PDMS-PGLY-09) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), GMMA,HEMA, Daracure 1173, and water as shown in Table 7. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lensexhibited phase separation and had a clarity rank of 7. The preparedcontact lenses had an average diameter of 15.45 mm. The prepared contactlenses had an oxygen permeability (D_(k)) of 63.

Example 36 (PDMS-PGLY-10)

A formulation (PDMS-PGLY-10) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), GMMA,NVP, and Daracure 1173 as shown in Table 7. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lenshad a clarity rank of 5. The prepared contact lenses had an averagediameter of 18 mm.

TABLE 7 Formulations containing modified PDMS-Polyglycerol. ExampleExample Example Example Example 32 33 34 35 36 (PDMS- (PDMS- (PDMS-(PDMS- (PDMS- PGLY-06) PGLY-07) PGLY-08) PGLY-09) PGLY-10) MaterialsPercent Percent Percent Percent Percent AC-CE- 39.40 35.48 31.52 14.7919.70 (PDMS- PGLY) (Macromer- 26) GMMA 39.40 35.48 31.52 44.37 59.11HEMA 0.00 0.00 0.00 14.79 0.00 NVP 19.70 17.74 15.76 0.00 19.70Initiator 1.50 1.35 1.20 1.11 1.48 (Daracure 1173) water 0.00 10.0020.00 24.94 0.00 Total 100 100 100 100 100 Formulation clear clear clearclear clear Before Cure Lens Phase Phase Phase Phase — Appearanceseparation separation separation separation Lens Clarity — 8 6 7 5 RankLens ~15 14-14.2 14.0-14.20 15.40- 17.50- Diameter 15.50 18.50 (mm)Average — 14.1 14.1 15.45 18 Diameter Dk — — 64 63 — AC-CE-(PDMS-PGLY)was prepared according to procedure described in Example 26; LensClarity Rank is from 1 to 10, with 1 being the worst (completelyopaque); Dk = Oxygen permeability of a contact lens is abbreviated,where “D” is diffusivity (cm²/sec) and “k” is the solubility of oxygenin a given contact lens material (ml O²/ml of material × mm Hg); Contactlenses were prepared by UV curing in a nitrogen flushed chamber usingspin cast technology as described above.

Example 37 (PDMS-PGLY-11)

A formulation (PDMS-PGLY-11) was prepared by combining AC-CE-PDMS-PGLY(prepared according to the procedure described in Example 26), GMMA,NVP, and Daracure 1173 as shown in Table 8. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lenshad a clarity rank of 6. The prepared contact lenses had an averagediameter of 15.45 mm.

Example 38 (PDMS-PGLY-12)

A formulation (PDMS-PGLY-12) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), GMMA,NVP, and Daracure 1173 as shown in Table 8. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lenshad a clarity rank of 10. The prepared contact lenses had an averagediameter of 15.55 mm.

Example 39 (PDMS-PGLY-13)

A formulation (PDMS-PGLY-13) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), GMMA,NVP, and Daracure 1173 as shown in Table 8. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lenshad a clarity rank of 10. The prepared contact lenses had an averagediameter of 13.45 mm.

Example 40 (PDMS-PGLY-14)

A formulation (PDMS-PGLY-14) was prepared by combining AC-CE-PDMS-PGLY(prepared according to the procedure described in Example 26), GMMA,NVP, and Daracure 1173 as shown in Table 8. Before curing, theformulation was clear. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contact lenshad a clarity rank of 9. The prepared contact lenses had an averagediameter of 16.75 mm.

Example 41 (PDMS-Gly-22)

A formulation (PDMS-Gly-22) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP, andDaracure 1173 as shown in Table 9. Contact lenses were then preparedfrom the formulation using spin cast technology with UV cure in anitrogen flushed UV light chamber, as described above. The preparedcontact lenses were clear with no phase separation. The prepared contactlenses had a diameter of 14.6 mm. The prepared contact lenses were toofragile to measure the oxygen permeability (Dk). The prepared contactlenses had a water percentage of 67%.

TABLE 8 Formulations containing modified PDMS-Polyglycerol. ExampleExample Example Example 37 38 39 40 (PDMS- (PDMS- (PDMS- (PDMS- PGLY-11)PGLY-12) PGLY-13) PGLY-14) Materials Percent Percent Percent PercentAC-CE- 28.15 24.63 39.53 16.42 PDMS- PGLY (Macromer- 26) GMMA 42.2224.63 19.76 49.26 NVP 28.15 49.26 39.53 32.84 Initiator 1.48 1.48 1.191.48 (Daracure 1173) Total 100 100 100 100 Formulation clear clear clearclear Before Cure Lens Clarity 6 10 10 9 Rank Lens 15.40 to 15.50 to13.40 to 16.50 Diameter 15.50 mm 15.60 mm 13.50 mm to 17 mm (mm) Average15.45 15.55 13.45 16.75 Diameter AC-CE-PDMS-PGLY used in the aboveformulations was prepared according to the procedure described inExample 26 Lens Clarity Rank is from 1 to 10, with 1 being the worst(completely opaque) Contact lenses were prepared by UV curing in anitrogen flushed chamber using spin cast technology as described above

Example 42 (PDMS-Gly-23)

A formulation (PDMS-Gly-23) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,3-Methacryloxy-2-Hydroxypropoxy(propylbis(trimethylsilyloxy)-methylsilane(SIGMA), GMMA, polyvinylpyrrolidone (PVP), and Daracure 1173 as shown inTable 9. Contact lenses was then prepared from the formulation usingspin cast technology with UV cure in a nitrogen flushed UV lightchamber, as described above. The prepared contact lenses exhibited aslight phase separation. The prepared contact lenses had a diameter of14.6 mm. The prepared contact lenses had an oxygen permeability (Dk) of62.13×10⁻¹¹ and a water percentage of 66.3%.

Example 43 (PDMS-PGLY-24)

A formulation (PDMS-PGLY-24) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 9. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear with no phase separation. Theprepared contact lenses had a diameter of 14.2-14.3 mm. The preparedcontact lenses had an oxygen permeability (Dk) of 101.43×10⁻¹¹ and awater percentage of 65.4%.

Example 44 (PDMS-PGLY-25)

A formulation (PDMS-PGLY-25) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,3-Methacryloxy-2-Hydroxypropoxy(propylbis(trimethylsilyloxy)-methylsilane(SIGMA), GMMA, polyvinylpyrrolidone (PVP), and Daracure 1173 as shown inTable 9. Contact lenses were then prepared from the formulation usingspin cast technology with UV cure in a nitrogen flushed UV lightchamber, as described above. The prepared contact lenses were clear withno phase separation. The prepared contact lenses had a diameter of13.3-13.4 mm. The prepared contact lenses had an oxygen permeability(Dk) of 78.35×10⁻¹¹ and a water percentage of 56.5%.

Example 45 (PDMS-Gly-25A)

A formulation (PDMS-Gly-25A) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 10. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses had slight phase separation but were less cloudythan Example 42 (PDMS-Gly-23). The prepared contact lenses had adiameter of 13.30 mm. The prepared contact lenses had an oxygenpermeability (Dk) of 80.04×10⁻¹¹ and a water percentage of 57.3%.

Example 46 (PDMS-PGLY-28)

A formulation (PDMS-PGLY-28) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, and Daracure 1173 as shown in Table 10. Contact lenses were thenprepared from the formulation using spin cast technology with UV cure ina nitrogen flushed UV light chamber, as described above. The preparedcontact lenses were opaque. The prepared contact lenses had a diameterof 13.8-13.85 mm. The prepared contact lenses had an oxygen permeability(Dk) of 92.59×10⁻¹¹ and a water percentage of 64%.

TABLE 9 Formulations containing modified PDMS-Polyglycerol. Example 41Example 42 Example 43 Example 44 (PDMS- (PDMS- (PDMS- (PDMS- Gly-22)Gly-23) PGLY-24) PGLY-25) Materials Percent Percent Percent PercentAC-CE- 59.17 24.44 22.22 24.66 (PDMS- PGLY) (Macromer- 26) NVP 39.4536.66 44.44 24.66 SIGMA 0.00 12.22 22.22 24.66 GMMA 0.00 24.44 1.4224.66 PVP 0.00 0.88 8.33 0.00 Initiator 1.38 1.37 1.38 1.35 (Daracure1173) Total 100.0 100.0 100.0 100.0 Lens Clear Lens Slight phase Clearlens Clear lens Clarity No Phase separation No phase No phase Separationseparation separation Lens 14.6 14.6 14.20-14.30 13.3-13.40 Diameter(mm) Dk Too fragile to 62.13 × 101.43 × 78.35 × measure 10⁻¹¹ 10⁻¹¹10⁻¹¹ % Water 67 66.3 65.4 56.5 AC-CE-(PDMS-PGLY) used in the aboveformulations was prepared according to procedure described in Example26; Lens Clarity Rank is from 1 to 10, with 1 being the worst(completely opaque); Dk = Oxygen permeability of a contact lens isabbreviated, where “D” is diffusivity (cm²/sec) and “k” is thesolubility of oxygen in a given contact lens material (ml O₂/ml ofmaterial × mm Hg); Contact lenses were prepared by UV curing in anitrogen flushed chamber using spin cast technology as described above.

Example 47 (PDMS-PGLY-29)

A formulation (PDMS-PGLY-29) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, PVP, and Daracure 1173 as shown in Table 10. Contact lenses werethen prepared from the formulation using spin cast technology with UVcure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were opaque. The prepared contact lenses had adiameter of 14.40-14.45 mm. The prepared contact lenses had an oxygenpermeability (Dk) of 127.01×10⁻¹¹ and a water percentage of 64.7%.

Example 48 (PDMS-Gly-30)

A formulation (PDMS-Gly-30) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, PVP, and Daracure 1173 as shown in Table 10. Contact lenses werethen prepared from the formulation using spin cast technology with UVcure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were opaque. The prepared contact lenses had adiameter of 15.20-15.25 mm. The prepared contact lenses had an oxygenpermeability (Dk) of 109.36×10⁻¹¹ and a water percentage of 68.7%.

Example 49 (PDMS-PGLY-31)

A formulation (PDMS-PGLY-31) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, PVP, and Daracure 1173 as shown in Table 11. Contact lenses werethen prepared from the formulation using spin cast technology with UVcure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were opaque.

Example 50 (PDMS-PGLY-32)

A formulation (PDMS-PGLY-32) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, PVP, and Daracure 1173 as shown in Table 11. Contact lenses werethen prepared from the formulation using spin cast technology with UVcure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were opaque.

Example 51 (PDMS-PGLY-33)

A formulation (PDMS-PGLY-33) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, PVP, and Daracure 1173 as shown in Table 11. Contact lenses werethen prepared from the formulation using spin cast technology with UVcure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were opaque.

Example 52 (PDMS-PGLY-34)

A formulation (PDMS-PGLY-34) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 11. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear and exhibited no phase separation.The prepared contact lenses had a diameter of 14.7 mm. The preparedcontact lenses had an oxygen permeability (Dk) of 94.64×10⁻¹¹ and awater percentage of 69.9%.

TABLE 10 Formulations containing modified PDMS-Polyglycerol. Example 45Example 46 Example 47 Example 48 (PDMS- (PDMS- (PDMS- (PDMS- Gly-25A)PGLY-28) PGLY-29) Gly-30) Materials Percent Percent Percent PercentAC-CE- 24.45 24.66 24.44 24.45 (PDMS- PGLY) (Macromer- 26) NVP 24.4549.32 48.88 48.90 SIGMA 24.45 24.66 24.44 24.45 GMMA 24.45 0.00 0.000.00 PVP 0.88 0.00 0.88 0.88 Initiator 1.34 1.35 1.34 1.34 (Daracure1173) Total 100.0 100.0 100.0 100.0 Lens Slight Phase Opaque lens Opaquelens Opaque lens Clarity separation, but less cloudy than PDMS-Gly-23Lens 13.30 13.80-13.85 14.40-14.45 15.20-15.25 Diameter (mm) Dk 80.04 ×92.59 × 127.01 × 109.36 × 10⁻¹¹ 10⁻¹¹ 10⁻¹¹ 10⁻¹¹ % Water 57.3 64 64.768.7 AC-CE-(PDMS-PGLY) used in the above formulations was preparedaccording to procedure described in Example 26; Lens Clarity Rank isfrom 1 to 10, with 1 being the worst (completely opaque); Dk = Oxygenpermeability of a contact lens is abbreviated, where “D” is diffusivity(cm²/sec) and “k” is the solubility of oxygen in a given contact lensmaterial (ml O₂/ml of material × mm Hg); Contact lenses were prepared byUV curing in a nitrogen flushed chamber using spin cast technology asdescribed above.

TABLE 11 Formulations containing modified PDMS-Polyglycerol. Example 49Example 50 Example 51 Example 52 (PDMS- (PDMS- (PDMS- (PDMS- PGLY-31)PGLY-32) PGLY-33) PGLY-34) Materials Percent Percent Percent PercentAC-CE- 24.45 24.45 24.45 22.37 (PDMS- PGLY) (Macromer- 26) NVP 48.8948.89 48.89 44.74 SIGMA 24.45 24.45 24.45 22.37 GMMA 0.00 0.00 0.00 8.39PVP 0.88 0.88 0.88 0.78 Initiator 1.34 1.34 1.35 1.35 (Daracure 1173)Total 100.0 100.0 100.0 100.0 Lens Opaque lens Opaque lens Opaque lensClear lens - Clarity No phase separation Lens — — — 14.7 Diameter (mm)Dk — — — 94.64 × 10⁻¹¹ % Water — — — 69.9 AC-CE-(PDMS-PGLY) used in theabove formulations was prepared according to procedure described inExample 26; Lens Clarity Rank is from 1 to 10, with 1 being the worst(completely opaque); Dk = Oxygen permeability of a contact lens isabbreviated, where “D” is diffusivity (cm²/sec) and “k” is thesolubility of oxygen in a given contact lens material (ml O₂/ml ofmaterial × mm Hg); Contact lenses were prepared by UV curing in anitrogen flushed chamber using spin cast technology as described above.

Example 53 (PDMS-PGLY-35)

A formulation (PDMS-PGLY-35) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 12. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear and exhibited no phase separation.The prepared contact lenses had a diameter of 13.80-13.85 mm. Theprepared contact lenses had an oxygen permeability (Dk) of 84.26×10⁻¹¹and a water percentage of 66.1%.

Example 54 (PDMS-PGLY-36)

A formulation (PDMS-PGLY-36) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 12. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear and exhibited no phase separation.The prepared contact lenses had a diameter of 13.8 mm. The preparedcontact lenses had an oxygen permeability (Dk) of 72.94×10⁻¹¹ and awater percentage of 66.9%.

Example 55 (PDMS-PGLY-37)

A formulation (PDMS-PGLY-37) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 12. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear and exhibited no phase separation.The prepared contact lenses had a diameter of 14.00-14.10 mm and a basecurve of 8.65 to 8.80 mm. The prepared contact lenses had an oxygenpermeability (Dk) of 90×10⁻¹¹ barrer and a water content percentage of66%.

Example 56 (PDMS-PGLY-38)

A formulation (PDMS-PGLY-38) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 12. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear and exhibited no visible indicationsof phase separation.

Example 57 (PDMS-PGLY-39)

A formulation (PDMS-PGLY-39) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 13.

Example 58 (PDMS-PGLY-40)

A formulation (PDMS-PGLY-40) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 13.

TABLE 12 Formulations containing modified PDMS-Polyglycerol. Example 53Example 54 Example 55 Example 56 (PDMS- (PDMS- (PDMS- (PDMS- PGLY-35)PGLY-36) PGLY-37) PGLY-38) Materials Percent Percent Percent PercentAC-CE- 31.32 35.79 22.37 22.37 (PDMS- PGLY) (Macromer- 26) NVP 35.7935.79 40.26 35.79 SIGMA 22.37 17.90 26.84 31.32 GMMA 8.39 8.39 8.39 8.39PVP 0.78 0.78 0.78 0.78 Initiator 1.35 1.35 1.35 1.36 (Daracure 1173)Total 100.0 100.0 100.0 100.0 Lens Clear lens - Clear lens - Clearlens - Clear lens - Clarity No phase No phase No phase No phaseseparation separation separation; separation Lens 13.80-13.85 13.814.00-14.10 — Diameter (mm) Dk 84.26 × 10⁻¹¹ 72.94 × 10⁻¹¹ 90 × 10⁻¹¹; —% Water 66.1 66.9 66 — AC-CE-(PDMS-PGLY) used in the above formulationswas prepared according to procedure described in Example 26; LensClarity Rank is from 1 to 10, with 1 being the worst (completelyopaque); Dk = Oxygen permeability of a contact lens is abbreviated,where “D” is diffusivity (cm²/sec) and “k” is the solubility of oxygenin a given contact lens material (ml O₂/ml of material × mm Hg); Contactlenses were prepared by UV curing in a nitrogen flushed chamber usingspin cast technology as described above.

Example 59 (PDMS-PGLY-41)

A formulation (PDMS-PGLY-41) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 13.

Example 60 (PDMS-Gly-42)

A formulation (PDMS-Gly-42) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 13. Contact lenseswere then prepared from the formulation using spin cast technology witha UV cure in a nitrogen flushed UV light chamber, as described above.The prepared contact lenses were clear and exhibited no phaseseparation. The prepared contact lenses had a diameter of 13.90-13.95mm. The prepared contact lenses had an oxygen permeability (Dk) of61.55×10⁻¹¹ and a water percentage of 62%.

Example 61 (PDMS-PGLY-44)

A formulation (PDMS-PGLY-44) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 14. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear and exhibited no phase separation.The prepared contact lenses had a diameter of 14.30-14.35 mm. Theprepared contact lenses had an oxygen permeability (Dk) of 85.59×10⁻¹¹and a water percentage of 67.5%.

Example 62 (PDMS-PGLY-45)

A formulation (PDMS-PGLY-45) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 14. Contact lenseswere then prepared from the formulation using spin cast technology withUV cure in a nitrogen flushed UV light chamber, as described above. Theprepared contact lenses were clear and exhibited no phase separation.The prepared contact lenses had a diameter of 14.40-14.45 mm. Theprepared contact lenses had an oxygen permeability (Dk) of 100.32×10⁻¹¹and a water percentage of 68%.

Example 63 (PDMS-PGLY-46)

A formulation (PDMS-PGLY-46) was prepared by combining AC-CE-(PDMS-PGLY)(prepared according to the procedure described in Example 26), NVP,SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table 14. Contact lenseswere then prepared from the formulation using spin cast technology witha UV cure in a nitrogen flushed UV light chamber, as described above.The prepared contact lenses were clear and exhibited no phaseseparation. The prepared contact lenses had a diameter of 14.20-14.25mm. The prepared contact lenses had an oxygen permeability (Dk) of85.05×10⁻¹¹ and a water percentage of 67%.

TABLE 13 Formulations containing modified PDMS-Polyglycerol. Example 57Example 58 Example 59 Example 60 (PDMS- (PDMS- (PDMS- (PDMS- PGLY-39)PGLY-40) PGLY-41) Gly-42) Materials Percent Percent Percent PercentAC-CE- 22.37 26.85 31.31 22.37 (PDMS- PGLY) (Macromer- 26) NVP 35.7931.32 31.31 33.55 SIGMA 31.32 31.32 26.84 26.84 GMMA 8.39 8.39 8.3915.10 PVP 0.78 0.78 0.78 0.78 Initiator 1.35 1.35 1.35 1.36 (Daracure1173) Total 100.0 100.0 100.00 100.0 Lens — — — Clear lens - Clarity NoPhase Separation Lens — — — 13.90-13.95 Diameter (mm) Dk — — — 61.55 ×10⁻¹¹ % Water — — — 62 AC-CE-(PDMS-PGLY) used in the above formulationswas prepared according to procedure described in Example 26; LensClarity Rank is from 1 to 10, with 1 being the worst (completelyopaque); Dk = Oxygen permeability of a contact lens is abbreviated,where “D” is diffusivity (cm²/sec) and “k” is the solubility of oxygenin a given contact lens material (ml O₂/ml of material × mm Hg); Contactlenses were prepared by UV curing in a nitrogen flushed chamber usingspin cast technology as described above.

TABLE 14 Formulations containing modified PDMS-Polyglycerol. Example 61Example 62 Example 63 (PDMS-PGLY-44) (PDMS-PGLY-45) (PDMS-PGLY-46)Materials Percent Percent Percent AC-CE- 22.68 22.37 22.32 (PDMS- PGLY)(Macromer- 26) NVP 40.82 40.27 40.17 SIGMA 24.94 22.37 24.55 GMMA 10.7712.86 10.60 PVP 0.79 0.78 1.00 Initiator 1.38 1.36 1.35 (Daracure 1173)Total 100.0 100.0 100.0 Lens Clarity Clear lens - Clear lens - Clearlens - No Phase No Phase No Phase Separation Separation Separation Lens14.30-14.35 14.40-14.45 14.20-14.25 Diameter (mm) Dk 85.59 × 10⁻¹¹100.32 × 10⁻¹¹ 85.05 × 10⁻¹¹ % Water 67.5 68 67 AC-CE-(PDMS-PGLY) usedin the above formulations was prepared according to procedure describedin Example 26; Lens Clarity Rank is from 1 to 10, with 1 being the worst(completely opaque); Dk = Oxygen permeability of a contact lens isabbreviated, where “D” is diffusivity (cm²/sec) and “k” is thesolubility of oxygen in a given contact lens material (ml O₂/ml ofmaterial × mm Hg); Contact lenses were prepared by UV curing in anitrogen flushed chamber using spin cast technology as described above.

Example 64 (PDMS-PGLY-48)

A small scale amount (<1 gram) of a formulation (PDMS-PGLY-48) wasprepared by combining AC-CE-(PDMS-PGLY) (prepared according to theprocedure described in Example 26), NVP, SIGMA, GMMA, PVP, and Daracure1173 as shown in Table 15. Contact lenses were then prepared from theformulation using spin cast technology with UV cure in a nitrogenflushed UV light chamber, as described above. The prepared contactlenses were clear and exhibited no phase separation. The preparedcontact lenses had a diameter of 14.15-14.20 mm. The prepared contactlenses had an oxygen permeability (Dk) of 91.02×10⁻¹¹ and a waterpercentage of 66.7%.

Example 65 (PDMS-PGLY-48A)

A formulation was prepared by combining 25 grams of macromer,AC-CE-(PDMS-PGLY) (prepared according to the procedure described inExample 26), NVP, SIGMA, GMMA, PVP, and Daracure 1173 as shown in Table15. Contact lenses were then prepared from the formulation using spincast technology with UV cure in a nitrogen flushed UV light chamber, asdescribed above. The prepared contact lenses were clear and exhibited nophase separation. The prepared contact lenses had a diameter of14.15-14.20 mm

TABLE 15 Formulations containing modified PDMS-Polyglycerol. Example 64Example 65 (PDMS-PGLY-48) (PDMS-PGLY-48A) Percent Percent AC-CE-(PDMS-22.62 22.62 PGLY) (Macromer-26) NVP 37.33 37.33 SIGMA 24.89 24.89 GMMA13.01 13.01 PVP 0.79 0.79 Initiator (Daracure 1.37 1.37 1173) Total100.0 100.0 Lens Clarity Clear lens - No Phase Clear lens - No PhaseSeparation Separation Lens Diameter (mm) 14.15-14.20 14.15-14.20 Dk97.02 × 10⁻¹¹ — % Water 66.7 — AC-CE-(PDMS-PGLY) used in the aboveformulations was prepared according to procedure described in Example26; Lens Clarity Rank is from 1 to 10, with 1 being the worst(completely opaque); Dk = Oxygen permeability of a contact lens isabbreviated, where “D” is diffusivity (cm²/sec) and “k” is thesolubility of oxygen in a given contact lens material (ml O₂/ml ofmaterial × mm Hg); Contact lenses were prepared by UV curing in anitrogen flushed chamber using spin cast technology as described above.

Example 66

A formulation (1002-138-1F-1) was prepared by combining macromerAC-(PDMS-PGLY) (prepared according to procedure given in example 1) withvarious monomers, as shown in Table 16. A portion of the sample wasplaced in a plastic cap (˜30 mm diameter) and exposed to UVA (3 mW/cm²)for about 10-15 minutes. The viscosity of this formulation increasedafter exposure to UVA, but it did not form a discernable gel under theseconditions.

Example 67

A formulation (1002-138-1-F-2) was prepared by combining macromerAC-(PDMS-PGLY) (prepared according to procedure given in example 1) withvarious monomers, as shown in Table 16. A portion of the sample wasplaced in a plastic cap (˜30 mm diameter) and exposed to UVA (3 mW/cm²)for about 10-15 minutes to yield a clear gel.

Example 68

Formulation 1002-138-1-F-4 was prepared by combining 15.02 grams offormulation 1002-138-1-F-3 with 0.005 grams of AMA, 0.005 grams ofDaracure 1173, and 21.15 grams of isopropanol. Mass of individualcomponents in listed in formulation 1002-138-1-F-4 shown in Table 16were calculated. A portion of the sample was placed in a plastic cap(˜30 mm diameter) and exposed to UVA (3.5 mW/cm²) for about 30 minutes.A discernable cross-linked gel did not form under these conditions.

Example 69

A formulation (1002-138-1-F-5) was prepared by combining macromerAC-(PDMS-PGLY) (prepared according to procedure given in example 1) withvarious monomers, as shown in Table 17. A portion of the formulation wasplaced in a plastic cap (˜30 mm diameter) and exposed to UVA (3 mW/cm²)for about 15 minutes to yield a clear gel. The gel was soaked in about 5mL isopropyl alcohol for about 15 minutes and then equilibrated inpurified water. The gel remained clear in its hydrated state and wasnoted to be lubricious and good elasticity. The gel was stretched toabout double its original length before breaking.

Example 70

A formulation (1002-142-1-F-1) was prepared by combining macromerAC-(PDMS-PGLY) (prepared according to procedure given in example 1) withvarious monomers, as shown in Table 17. About 0.3 mL portion of theformulation was placed in a plastic cap (˜30 mm diameter) and exposed toUVA (3 mW/cm²) for about 10 minutes to yield a clear gel. The gel wasfurther exposed to UVA for about 10 more minutes. The gel was soaked inabout 10 mL of isopropanol for about 10 minutes. The isopropanol wasdrained from the gel and replaced with fresh isopropanol. The gel wasfurther extracted by heating the isopropanol to about 60° C. for about15 minutes. The gel was then placed in purified water. The gel was notedto be opaque (white) and brittle.

TABLE 16 Evaluation of formulations containing actinicallycross-linkable polydimethylsiloxane-polyglycerol {AC-(PDMS-PGLY)}Example 66 Example 67 Example 68 (1002-138- (1002-138- (1002-138-1-F-4)1-F-1) 1-F-2) Grams Materials Grams Percent Grams Percent (calculated)Percent AC- 1.024 66.45 0.498 49.84 7.516 20.8 (PDMS- PGLY) (Macro-mer-1) SIGMA — — — — 3.726 10.3 GMMA — — 0.250 25.00 3.717 10.3 NVP — —— — — — AMA — — — — 0.005 — Daracure 0.016 1.04 0.008 0.78 0.067 0.21173 IPA 0.501 32.51 0.244 24.38 21.15 58.5 Total 1.541 100 1.000 10036.181 100 AC-(PDMS-PGLY) (1002-138-1) used in the above formulationswas prepared as described in example 1.

Example 71

A formulation (1002-142-1-F-2) was prepared by combining 7.506 grams offormulation 1002-142-1-F-1 with 1.104 grams of NVP. Mass of individualcomponents in listed in formulation 1002-142-1-F-2 shown in Table 17were calculated. About 0.3 mL portion of the above formulation wasplaced in a plastic cap (˜30 mm diameter) and exposed to UVA (3 mW/cm²)for about 10 minutes to yield a clear and tacky gel. Additional curingfor 20 minutes (total cure time of 30 minutes) yielded a semiflexiblegel. The gel was hydrated in purified water and was noted to be brittleand opaque (white).

Example 72 (1002-138-3-F1)

A formulation was prepared by combining 1.048 grams of macromer-2(prepared according to procedure given in example 2) with 0.046 grams ofDaracure 1173 and 0.375 grams of isopropyl alcohol. The resultingformulation was noted to be cloudy and was not subjected to curetesting.

TABLE 17 Evaluation of formulations containing actinicallycross-linkable polydimethylsiloxane-polyglycerol {AC-(PDMS-PGLY)}Example 69 Example 70 Example 71 (1002-138- (1002-142- (1002-142-1-F-2)1-F-5) 1-F-1) Grams Materials Grams Percent Grams Percent (calculated)Percent AC-(PDMS- 7.60 21.0 7.63 46.8 3.513 46.8 PGLY) (Macromer −1)SIGMA 3.77 10.4 4.61 28.3 2.124 28.3 GMMA 0.00 0.0 0.00 0.0 0.000 0 NVP3.71 10.2 3.92 24.0 2.905 24 AMA 0.08 0.2 0.08 0.5 0.038 0.5 Daracure0.08 0.2 0.08 0.5 0.038 0.5 1173 Total 36.181 100 16.30 100.0 7.506 100AC-(PDMS-PGLY) (1002-138-1) used in the above formulations was preparedas described in example 1.

Example 73 (1002-156-2)

A formulation (1002-156-2) was prepared by combining 1.520 grams ofMacromer-26 (macromer prepared as described in Example 26), 1.051 gramsof macromer-5 (macromer prepared as described in example 5), 0.058 gramsAMA, and about 10 microliters (calculated 0.011 grams) of Daracure 1173,as shown in Table 18, to yield a hazy fluid. Upon addition of 6.5 gramst-amyl alcohol (tAA), the formulation became clear. This formulationformed a gel when exposed to UVA. Hydration of the UV cured sample inpurified water, yielded a lubricous gel with a hazy appearance.

Example 74 (1002-156-3)

A formulation (1002-156-3) was prepared by combining 1.252 grams ofMacromer-26 (prepared as described in Example 26), 1.253 grams ofmacromer-4 (prepared as described in Example 4), and about 10microliters (calculated 0.011 grams) of Daracure 1173 as shown in Table18. The prepared formulation was hazy. Upon addition of 8.5 grams t-amylalcohol (tAA), the formulation became clear. To further test theformulation, a cure test was performed as described for Example 73.After hydration, a hazy, lubricous gel was obtained.

Example 75 (1002-156-4)

A formulation (1002-156-4) was prepared by combining 1.251 grams ofmacromer-26 (prepared as described in Example 26), 1.254 grams ofmacromer-4 (prepared as described in Example 4), 0.015 grams AMA, andabout 10 microliters (calculated 0.011 grams) of Daracure 1173 as shownin Table 18 to yield a hazy fluid. Addition of SIGMA monomer (14.5grams) did not improve miscibility. No further tests were performed onthis formulation.

TABLE 18 Evaluation of actinically cross-linkable formulationscontaining allyl methacrylate, SIGMA and chain extended PDMS-Polyglycerol Modified PDMS-Polyglycerol Example 73 Example 74 Example 75(1002-156-2) (1002-156-3) (1002-156-4) Percent Percent PercentFormulation by by by Components Grams Weight Grams Weight Grams WeightMacromer-26 1.520 16.63 1.252 11.48 1.251 7.35 Macromer-4 0 0 1.25311.48 1.254 7.36 Macromer-5 1.051 11.5 0 0 0 0 Macromer-6 0 0 0 0 0 0Macromer-7 0 0 0 0 0 0 AMA 0.058 0.63 0 0 0.015 0.09 SIGMA 0 0 0 014.501 85.14 t-amyl alcohol 6.5 71.12 8.5 76.94 0 0 Daracure 1173 0.0110.12 0.011 0.1 0.011 0.06 Total 9.140 100.00 10.917 100.00 17.032 100.00Appearance hazy before hazy before Cloudy before of formulation additionaddition addition of tAA of tAA of SIGMA Clarity of clear after clearafter Cloudy after Formulation after addition addition addition ofaddition of tAA of tAA of tAA SIGMA or SIGMA

Example 76 (1002-156-5)

A formulation (1002-156-5) was prepared by combining 1.029 grams ofmacromer-5 (prepared as described in Example 5), 1.114 grams ofmacromer-4 (prepared as described in Example 4), 0.059 grams AMA, andabout 10 microliters (calculated 0.011 grams) of Daracure 1173 as shownin Table 19 to yield a clear fluid. Upon addition of 7.5 grams t-amylalcohol (tAA) the formulation remained clear. This formulation was thenexposed to UVA. Hydration of the UV cured sample in purified wateryielded a lubricous gel with a hazy appearance.

Example 77 (1002-156-6)

A formulation (1002-156-6) was prepared by combining 1.252 grams ofMacromer-26 (prepared as described in Example 26), with 1.250 grams ofmacromer-6 (prepared as described in Example 6), 0.065 grams AMA, andabout 10 microliters (calculated 0.011 grams) of Daracure 1173 as shownin Table 19 to yield a clear fluid. The formulation formed a gel whenexposed to UVA. Hydration of the UV cured sample in purified wateryielded a lubricous gel with a partly hazy appearance.

Example 78 (1002-156-7)

A formulation (1002-156-7) was prepared by combining 1.253 grams ofMacromer-26 (prepared as described in Example 26), 1.258 grams ofmacromer-7 (prepared as described in Example 7), and about 10microliters (calculated 0.011 grams) of Daracure 1173 as shown in Table19 to yield a clear fluid. The formulation formed a gel when exposed toUVA. Hydration of the UV cured sample in purified water yielded a clearlubricous gel with a white outer ring.

Example 79 (1002-154-4)

A formulation (1002-154-4) was prepared by combiningpolydimethylsiloxane (KF6100, Viscosity ˜40,000 cps), and isophoronediisocyanate (IPDI) containing 0.1 mg DBTDL/mL as shown in Table 20.

Example 80 (1002-154-5)

A formulation (1002-154-5) was prepared by combiningpolydimethylsiloxane (KF6100, Viscosity ˜40,000 cps), isophoronediisocyanate (IPDI) containing 0.1 mg DBTDL/mL, and diethylene glycol asshown in Table 20.

Example 81 (1002-154-6)

A formulation (1002-154-6) was prepared by combiningpolydimethylsiloxane (KF6100, Viscosity ˜40,000 cps), isophoronediisocyanate (IPDI) containing 0.1 mg DBTDL/mL, and diethylene glycol asshown in Table 20.

Example 82 (1002-154-3)

A formulation (1002-154-3) was prepared by combining macromer-4(prepared as described in Example 4) and IPA containing 3.33 mg IRGACUREas shown in Table 21. The sample was spread on a polyethylene sheet andexposed to UV irradiation (3.5 mW/cm²) for 30 minutes. Upon UV exposure,the sample thickened but did not gel.

TABLE 19 Evaluation of actinically cross-linkable formulationscontaining allyl methacrylate, SIGMA and chain extendedPDMS-Polyglycerol Modified PDMS-Polyglycerol Example 76 Example 77Example 78 (1002-156-5) (1002-156-6) (1002-156-7) Percent by Percent byPercent by Formulation Components Grams Weight Grams Weight Grams WeightMacromer-26 0 0 1.252 48.56 1.253 49.69 Macromer-4 1.114 11.47 0 0 0 0Macromer-5 1.029 10.59 0 0 0 0 Macromer-6 0 0 1.250 48.49 0 0 Macromer-70 0 0 0 1.258 49.89 AMA 0.059 0.61 0.065 2.52 0 0 SIGMA 0 0 0 0 0 0t-amyl alcohol 7.5 77.22 0 0 0 0 Daracure 1173 0.011 0.11 0.011 0.420.011 0.43 Total 9.713 100.00 2.578 99.99 2.522 100.00 Appearance offormulation clear clear clear Clarity of Formulation after N/A N/A N/Aaddition of tAA or SIGMA

TABLE 20 PDMS-Polyglycerol Copolymerized with diisocyanate anddiethyleneglycol. Example 79 Example 80 Example 81 (1002-154-4)(1002-154-5) (1002-154-6) Materials Grams Percent Grams Percent GramsPercent KF6100 5.3 91.22 5.01 69.68 5.35 57.04 IPDI containing 0.1 mgDBTDL/mL 0.51 8.78 1.08 15.02 2.02 21.54 Diethylene glycol 0.00 0.001.10 15.30 2.01 21.43 Total 5.81 100 7.19 100 9.38 100

TABLE 21 Evaluation of actinically curable formulation containingPDMS-Polyglycerol copolymer dissolved in IPA. Example 82 (1002-154-3)Materials Actual Grams Percent 1002-152-1 (98.43% KF6100-1.58% IEM) 3.570.1 IPA containing 3.33 mg Irgacurc 2951/ml 1.49 29.9 Total 4.99 100

TABLE 22 Diameter of contact lenses after repeated autoclavesterilization at 121° C. using +3.00 diopter contact lenses. AutoclavedAutoclaved Autoclaved Autoclaved Autoclaved Test 1× 2× 3× 4× 5× DiameterMean 14.32 14.32 14.33 14.38 14.39 (mm) Maximum 14.40 14.35 14.35 14.4014.40 Minimum 14.30 14.30 14.30 14.35 14.35 Range 0.10 0.05 0.05 0.050.05 (Max-Min) Standard 0.03 0.02 0.03 0.03 0.02 Deviation Power Average+3.00 +3.00 +3.00 +3.00 +3.00 (D) Maximum +3.00 +3.00 +3.00 +3.00 +3.00Minimum +3.00 +3.00 +3.00 +3.00 +3.00 Range 0.00 0.00 0.00 0.00 0.00(Max-Min) Standard 0.00 0.00 0.00 0.00 0.00 Deviation

Heat Stability of Contact Lenses (Example 83)

A formulation with about the same composition as described in Example 64was used to produce contact lenses. Contact lenses with different powerswere prepared using polypropylene molds and a spin cast UV-Cure processas described above. Contact lenses were removed from molds, extracted inan aqueous-ethanol solution, extracted in purified water, and placed inpolypropylene blisters containing buffered saline. The blisterscontaining the contact lenses immersed in buffered saline were heatsealed with foil lidding and subjected to repeated (1×, 2×, 3×, 4×, 5×)autoclave sterilization at about 121° C. Results from these tests (Table22-Table 25) show the contact lenses were stable to repeated autoclavesterilization.

TABLE 23 Contact lens diameter repeated autoclave sterilization at 121°C. using −3.25 diopter contact lenses. Autoclaved Autoclaved AutoclavedAutoclaved Autoclaved Test 1× 2× 3× 4× 5× Diameter Mean 14.51 14.5114.54 14.55 14.55 (mm) Maximum 14.55 14.55 14.55 14.60 14.60 Minimum14.40 14.40 14.50 14.50 14.50 Range 0.15 0.15 0.05 0.10 0.10 (Max-Min)Standard 0.04 0.04 0.02 0.03 0.03 Deviation Power Mean −3.25 −3.25 −3.25−3.25 −3.25 (D) Maximum −3.25 −3.25 −3.25 −3.25 −3.25 Minimum −3.25−3.25 −3.25 −3.25 −3.25 Range 0.00 0.00 0.00 0.00 0.00 (Max-Min)Standard 0.00 0.00 0.00 0.00 0.00 Deviation

TABLE 24 Base curve of contact lenses in Table 23 after repeatedautoclave sterilization. Autoclaved Autoclaved Autoclaved AutoclavedAutoclaved Test 1× 2× 3× 4× 5× Base Mean 8.94 8.99 9.00 9.00 8.99 CurveMaximum 9.00 9.00 9.05 9.05 9.00 (mm) Minimum 8.90 8.95 8.95 8.95 8.90Range 0.10 0.05 0.10 0.10 0.10 (Max-Min) Standard 0.05 0.02 0.03 0.030.03 Deviation Power Mean −3.25 −3.25 −3.25 −3.25 −3.25 (D) Maximum−3.25 −3.25 −3.25 −3.25 −3.25 Minimum −3.25 −3.25 −3.25 −3.25 −3.25Range 0.00 0.00 0.00 0.00 0.00 (Max-Min) Standard 0.00 0.00 0.00 0.000.00 Deviation

TABLE 25 Diameter of contact lenses after repeated autoclavesterilization at 121° C. using −8.25 diopter contact lenses. AutoclavedAutoclaved Autoclaved Autoclaved Autoclaved Test 1× 2× 3× 4× 5× DiameterMean 14.46 14.48 14.49 14.50 14.48 (mm) Maximum 14.55 14.55 14.55 14.6014.55 Minimum 14.30 14.25 14.25 14.25 14.25 Range 0.25 0.30 0.30 0.350.30 (Max-Min) Standard 0.09 0.09 0.10 0.11 0.09 Deviation Power Mean−8.25 −8.25 −8.25 −8.25 −8.25 (D) Maximum −8.25 −8.25 −8.25 −8.25 −8.25Minimum −8.25 −8.25 −8.25 −8.25 −8.25 Range 0.00 0.00 0.00 0.00 0.00(Max-Min) Standard 0.00 0.00 0.00 0.00 0.00 Deviation

Evaluation of Antifouling Properties (Example 84)

This example demonstrates that the materials described herein show goodresistance to fouling by protein. Contact lenses were prepared asdescribed in Example 28 and evaluated for Lysozyme depositionpropensity. For comparison, ionic contact lenses (etafilcon A) were alsoevaluated for Lysozyme deposition propensity. Three lenses were soakedseparately in ISO PBS and the ISO PBS was changed per hour (×3 times) towash away any surfactant. Before placing the lens in the respectivedeposition solution, the lens was wiped to remove any excess ISO PBS onthe lens. Each contact lens was then placed separately in 3×1.5 mL ofthe respective deposition solution in a glass vial. All the glass vialscontaining the lenses in deposition solution were incubated at 37° C.for 48 hours in water bath. After 48 hours, the vials were cooled toroom temperature and analyzed via the Bovine serum albumin assay (BSA).A standard BSA assay protocol is provided above. As a control, two glassvials containing the deposition solution without a contact lens werealso incubated using the same conditions above. The original depositionsolution and the solution after incubation in glass vial were analyzedvia BSA assay to ensure that there was no uptake of the protein solutionby the vial.

Using the BSA assay, a protein uptake of 1701 μg/mL was observed onClear58 contact lens and 413 μg/mL for Acuvue Moist contact lenses. BothClear58 and Acuvue Moist comprise etafilcon-A, which is an ionic highwater contact lenses (FDA group IV) material. Meanwhile, protein uptakefor a silicone hydrogel contact lens described herein was 3.78 μg/mL.

Example 85

A proton NMR spectrum of a cross-linkable polysiloxane-polyglycerolblock copolymer is shown in FIG. 4 .

An example crosslinkable polysiloxane-polyglycerol block copolymer asdisclosed herein is shown in Scheme 23.

Example 86—Stability Testing

The purpose of this example is to summarize the testing results forlenses at 15 months incubation. This example will discuss the resultsobtained at 15 month for lenses aged under accelerated aging conditionsat 45° C.

The scope of the report is limited to the 15 months incubation of thestability study of the soft silicone (Polyglyceryl-siloxane) hydrogelcontact lens. This report documents the results and analyses of testsexecuted in accordance with stability protocol S-STB-PTC-18-014.

Details of lenses which were used in the stability study are shown inTable 26.

TABLE 26 Monomer lot ID, lens lot number, back vertex power, date ofmanufacturing, and quantities of sample lenses that were produced andused in the stability study. Lens Formulation Lens Lens Back Vertex LotNo. Lot No. Lot ID Power 68GS-001 PGS0119001 A1 −8.25 PGS0119002 A2−3.25 PGS0119003 A3 +3.00 68GS-002 PGS0119004 A4 −8.25 PGS0119005 A5−3.25 PGS0119006 A6 +3.00 68GS-003 PGS0119007 A7 −8.25 PGS0119008 A8−3.25 PGS0119009 A9 +3.00

For the stability tests, The lenses were packaged in polypropylene bowls(S-cup), sealed with aluminum laminated foils and filled withphosphate-buffered saline (PBS). Total quantities of the above detailedstability samples were split and placed into three incubators maintainedat 25° C.±2° C., 35° C.±2° C. and 45° C.±2° C. Stability study resultsat baseline and previous intervals (3 months, 6 months, 9 months, and 12months) were also performed. The following tests were carried out in the15 month stability study: back vertex power; visual defect; diameter;back vertex radius of curvature; saline pH and osmolality; spectral andluminous transmittance; sterility test; water content; package sealintegrity; and extractables and biocompatibility studies. Lenses werecollected from 45° C. incubator for testing at 15 months interval. Thetemperature and humidity of incubators used in this stability study aresummarized in Table 27 and Table 28.

TABLE 27 Temperature of incubators from month 12 to month 15. IncubatorID/ Temperature Month 12 Month 13 Month 14 Month 15 Calibration Due Date(° C.) (° C.) (° C.) (° C.) (° C.) STL-ICU-09/ 45° C. Maximum 44 45 4645 Apr. 2, 2021 Minimum 43 43 44 44 Average 44 44 45 45

TABLE 28 Humidity of incubators from month 12 to month 15. Incubator ID/Calibration Due Date Humidity Month 12 Month 13 Month 14 Month 15STL-ICU-09/ 45° C. Maximum 38% 39% 39% 38% Apr. 2, 2021 Minimum 36% 36%37% 35% Average 37% 38% 38% 37%

The shelf life of the stability study can be accelerated by aging athigher temperature and the real time shelf life equivalent at 25° C. isestablished based on ISO 11987:2012 Clause 9.2.1, as summarized in Table29.

TABLE 29 Real time shelf life equivalent at 25° C. for contact lenssamples incubated under accelerated aging studies at 35° C. and 45° C.as per ISO 11987:2012 Clause 9.2.1. Real time shelf life equivalent at25° C. Incubation 25° C. ± 2° C. 35° C. ± 2° C. 45° C. ± 2° C. Period(real time) (accelerated) (accelerated)  0 months baseline  3 months 3months  6 months 12 months  6 months 6 months 12 months 24 months  9months 9 months 18 months 36 months 12 months 12 months  24 months 48months 15 months 15 months  30 months 60 months

The back vertex power of the lenses at 15 months was tested. Thespecification (e.g., acceptance criteria) identified for the test was±0.25 D of nominal value measured at baseline. The sampling plan for thetests was that 10 lenses per lens lot per test interval were sampled.The results of the back vertex power test of the lenses that met theacceptance criteria at 15 months are summarized in Table 30. In general,all the lens power are within manufacturing tolerances (i.e., ±0.25 D).

The visual defects of the lenses at 15 months was tested. Thespecification (e.g., acceptance criteria) identified for the test was nounusual color, surface deposit, and appearance. The sampling plan forthe tests was that 10 lenses per lens lot per test interval weresampled. The results of the visual defect test of the lenses that metthe acceptance criteria at 15 months are summarized in Table 31. Ingeneral, all the lenses did not have any visual defects.

TABLE 30 Results of the back vertex power test of the lenses that metthe acceptance criteria at 15 months. Monomer Lens Back Vertex Power (D)Lot No. Lot ID Baseline 15 months at 45° C. 68GS-001 A1 Mean −8.75 −8.81Range 0.13 0.25 SD 0.04 0.11 A2 Mean −3.50 −3.54 Range 0.50 0.25 SD 0.160.08 A3 Mean +3.00 +3.09 Range 0.50 0.25 SD 0.12 0.12 68GS-002 A4 Mean−8.75 −8.85 Range 0.25 0.25 SD 0.13 0.13 A5 Mean −3.75 −3.75 Range 0.250.00 SD 0.11 0.00 A6 Mean +3.00 +3.04 Range 0.25 0.25 SD 0.11 0.0868GS-003 A7 Mean −8.75 −8.79 Range 0.25 0.25 SD 0.12 0.08 A8 Mean −3.50−3.59 Range 0.25 0.25 SD 0.08 0.12 A9 Mean +3.00 +3.18 Range 0.25 0.25SD 0.12 0.12 Range = Maximum − minimum SD = Standard Deviation

TABLE 31 Results of the visual defect test of the lenses that met theacceptance criteria at 15 months. Monomer Lens Visual Defects Lot No.Lot ID Baseline 15 months at 45° C. 68GS-001 A1 No defects No defects A2No defects No defects A3 No defects No defects 68GS-002 A4 No defects Nodefects A5 No defects No defects A6 No defects No defects 68GS-003 A7 Nodefects No defects A8 No defects No defects A9 No defects No defects

The diameter of the lenses at 15 months was tested. The specification(e.g., acceptance criteria) identified for the test was a diameter of12.0-15.0 mm and ±0.20 mm of nominal value measured at baseline. 10lenses per lens lot per test interval were sampled. The results of thediameter test of the lenses that met the acceptance criteria at 15months are summarized in Table 32. In general, lens diameters are within±0.20 mm of nominal value measured at baseline.

The base curve of the lenses at 15 months was tested. The specification(e.g., acceptance criteria) identified for the test was a base curve of7.80-10.00 mm and ±0.20 mm of nominal value measured at baseline. Thesampling plan for the tests was that 10 lenses per lens lot per testinterval were sampled. The results of the base curve test of the lensesthat met the acceptance criteria at 15 months are summarized in Table33. In general, lens base curves are within ±0.20 mm of nominal valuemeasured at baseline.

The saline pH and osmolality of the lenses at 15 months was tested. Thespecification (e.g., acceptance criteria) identified for the test was apH of 6.30 to 8.50 and an osmolality of 285±65 mOsm·kg. The samplingplan for the tests was that the saline was pooled from 10 lenses permonomer lot per temperature condition per buy off for sampling. Theresults of the pH and Osmolality tests of the lenses that met theacceptance criteria at 15 months are summarized in Table 34. In general,the results of saline pH at 15 months are within specification and metthe acceptance criteria of the stability study. The saline pH value wasfound to be within ocular comfort range, which is around 6.3 to 8.5.

TABLE 32 Results of the diameter test of the lenses that met theacceptance criteria at 15 months. Monomer Lens Diameter (mm) Lot No. LotID Baseline 15 months at 45° C. 68GS-001 A1 Mean 14.10 14.13 Range 0.400.35 SD 0.15 0.12 A2 Mean 14.10 14.19 Range 0.33 0.30 SD 0.10 0.10 A3Mean 13.95 14.03 Range 0.13 0.25 SD 0.05 0.09 68GS-002 A4 Mean 14.0514.11 Range 0.23 0.25 SD 0.08 0.09 A5 Mean 14.10 14.22 Range 0.30 0.35SD 0.11 0.10 A6 Mean 14.05 14.10 Range 0.23 0.25 SD 0.07 0.11 68GS-003A7 Mean 14.05 14.05 Range 0.30 0.35 SD 0.10 0.10 A8 Mean 14.10 14.12Range 0.25 0.40 SD 0.09 0.15 A9 Mean 14.10 14.03 Range 0.25 0.30 SD 0.100.11 Range = Maximum − minimum SD = Standard Deviation

TABLE 33 Results of the base curve test of the lenses that met theacceptance criteria at 15 months. Monomer Lens Base curve (mm) Lot No.Lot ID Baseline 15 months at 45° C. 68GS-001 A1 Mean 8.60 8.45 Range0.15 0.10 SD 0.06 0.05 A2 Mean 8.60 8.71 Range 0.23 0.20 SD 0.08 0.05 A3Mean 8.50 8.66 Range 0.18 0.20 SD 0.05 0.06 68GS-002 A4 Mean 8.60 8.45Range 0.20 0.20 SD 0.06 0.07 A5 Mean 8.60 8.63 Range 0.25 0.20 SD 0.090.06 A6 Mean 8.55 8.65 Range 0.23 0.20 SD 0.07 0.08 68GS-003 A7 Mean8.60 8.50 Range 0.27 0.25 SD 0.12 0.07 A8 Mean 8.60 8.64 Range 0.25 0.30SD 0.09 0.08 A9 Mean 8.60 8.66 Range 0.20 0.25 SD 0.06 0.09 Range =Maximum − minimum SD = Standard Deviation

TABLE 34 Results of the saline pH and Osmolality test of the lenses thatmet the acceptance criteria at 15 months. Monomer Lot No. Test Baseline15 months at 45° C. 68GS-001 pH 7.46 7.48 Osmolality 254 268 (average;mOsm/kg) 68GS-002 pH 7.41 7.38 Osmolality 249 279 (average; mOsm/kg)68GS-003 pH 7.43 7.42 Osmolality 257 297 (average; mOsm/kg)

The spectral luminous transmittance of the lenses at 15 months wastested. The specification (e.g., acceptance criteria) identified for thetest was that the light transmittance of the lens measured between 380nm and 780 nm must be 95% T±5% T. The sampling plan for the tests wasthat 5 lenses (mid power) per monomer lot per temperature condition perbuy off were sampled. The results of the spectral and luminoustransmittance of the lenses that met the acceptance criteria at 15months are summarized in Table 35. In accordance with ISO 18369-3: 2006,visible light transmissibility of the lenses were to be measured forwavelength between 380 nm to 780 nm. Visible light transmissibility ofthe lenses was tested using Shimadzu UV-VIS spectra photometer UV-2450.The luminous transmittance was calculated from the spectraltransmittance value based on standard illuminant CIE A. The spectral andluminous transmittance of the light by the stability lenses at thevisible region is greater than 95%.

TABLE 35 Results of the spectral transmissibility at the visible regionfor the stability studies at 15 months. Visible Light TransmittanceMonomer Lot No. Baseline 15 months at 45° C. 68GS-001 99% T 99% T68GS-002 99% T 98% T 68GS-003 98% T 98% T

The sterility of the lenses at 15 months was tested. The specification(e.g., acceptance criteria) identified for the test was that the lenseswere sterile (no growth). The sampling plan for the tests was that 20lenses of any back vertex power per monomer lot per temperaturecondition per buy off were sampled. The results of the sterility testsof stability samples at 15 months are summarized in Table 36. Sterilityof the lenses was tested and met specification as per USP 32<71>.

TABLE 36 The sterility results of stability samples at 15 months.Monomer Sterility Lot No. Baseline 15 months at 45° C. 68GS-001 Nogrowth (sterile) No growth (sterile) 68GS-002 No growth (sterile) Nogrowth (sterile) 68GS-003 No growth (sterile) No growth (sterile)

The water content of the lenses at 15 months was tested. Thespecification (e.g., acceptance criteria) identified for the test wasthat the lenses has a water content of 68±2%. The sampling plan for thetests was that 25 lenses of any back vertex power per monomer lot pertemperature condition per buy off were sampled. The results of the lenswater content tests at 15 months that met the acceptance criteria aresummarized in Table 37. Water content of lens was tested as per ISO18369-4: 2006. The results of the tests show that the water content ofthe lens is within specification.

TABLE 37 Results of lens water content at 15 months. Monomer Lens WaterContent Lot No. Baseline 15 months at 45° C. 68GS-001 66% 67% 68GS-00266% 67% 68GS-003 67% 67%

The package integrity of the lenses at 15 months was tested (leak test).The specification (e.g., acceptance criteria) identified for thepackaging seal integrity test was that there was no leakage. Thesampling plan for the tests was that 10 blisters per back vertex powerper monomer per temperature condition per buy off were sampled. Theresults of the package seal integrity of stability samples at 15 monthsare summarized in Table 38. The blister packaged lenses that were sampletested at 15 months have no leakage and passed the dye penetration testby using Carleton Integrity Tester.

TABLE 38 Results of package seal integrity tests of stability samples at15 months. Monomer Lens Package Seal Integrity Lot No. Lot ID Baseline15 months at 45° C. 68GS-001 A1 No leakage No leakage A2 No leakage Noleakage A3 No leakage No leakage 68GS-002 A4 No leakage No leakage A5 Noleakage No leakage A6 No leakage No leakage 68GS-003 A7 No leakage Noleakage A8 No leakage No leakage A9 No leakage No leakage

The extractables and biocompatibility of the lenses were also tested.For cytotoxicity tests, the specification identified was that there wasacceptable cell lysis of toxicity as per ISO 10993-5. For ocularirritation tests, the specification identified was that there was anacceptable irritation scale as per ISO 10993-10. For systemic toxicitytests, the specification identified was that there was an acceptablebiological reactivity as per ISO 10993-11. For sensitization tests, thespecification identified was that there was an acceptable irritationscale as per ISO 10993-10. For extractables tests, the specificationidentified was for monitoring purposes.

The sampling plan for the biocompatibility tests was that 250 lenses permonomer lot (for 3 monomer lots) were sampled. The sampling plan for theextractables tests was that 110 lenses per monomer lot (for 2 monomerlots) were sampled. The results of the extractables and biocompatibilitystudies of stability samples at 15 months are summarized in Table 39.The results of the tests are within specifications and acceptancecriteria under ISO 10993 for cytotoxicity, ocular irritation,sensitization, and systemic toxicity.

In conclusion, the sample lenses incubated for 15 months underaccelerated aging conditions at 45° C. satisfied all testingspecifications and passed the acceptance criteria. 68GS's shelf life isdeclared as 5 years based on the results of accelerated aging at 45° C.at 15 months testing interval.

TABLE 39 Results of extractables and biocompatibility studies ofstability samples at 15 months Monomer Lot No. Lens Lot No. Test 15months at 45° C. 68GS-001 PGS0119003 Cytotoxicity Pass Ocular IrritationPass Systemic Toxicity Pass Sensitization Pass Extractables Water: Lessthan 0.1% (% m/m) Hexane: 0.12% 68GS-002 PGS0119006 Cytotoxicity PassOcular Irritation Pass Systemic Toxicity Pass Sensitization Pass68GS-003 PGS0119009 Cytotoxicity Pass Ocular Irritation Pass SystemicToxicity Pass Sensitization Pass Extractables Water: Less than 0.1% (%m/m) Hexane: 0.14%

The compositions and methods of the appended claims are not limited inscope by the specific compositions and methods described herein, whichare intended as illustrations of a few aspects of the claims and anycompositions and methods that are functionally equivalent are within thescope of this disclosure. Various modifications of the compositions andmethods in addition to those shown and described herein are intended tofall within the scope of the appended claims. Further, while onlycertain representative compositions and methods, and aspects of thesecompositions and methods are specifically described, other compositionsand methods and combinations of various features of the compositions andmethods are intended to fall within the scope of the appended claims,even if not specifically recited. Thus, a combination of steps,elements, components, or constituents can be explicitly mentionedherein; however, all other combinations of steps, elements, components,and constituents are included, even though not explicitly stated.

What is claimed is:
 1. A composition comprising anactinically-crosslinkable polysiloxane-polyglycerol block copolymerderived from: a polysiloxane prepolymer comprising a polyglycerol sidechain, the polyglycerol side chain comprising an ethylenicallyunsaturated group covalently linked thereto, wherein the ethylenicallyunsaturated group is actinically curable.
 2. The composition of claim 1,wherein the polysiloxane prepolymer is linear or branched.
 3. Thecomposition of claim 1, wherein the ethylenically unsaturated group iscovalently linked to the polyglycerol side chain directly or wherein theethylenically unsaturated group is covalently linked to the polyglycerolside chain through a linking group.
 4. The composition of claim 1,wherein the ethylenically unsaturated group comprises acryloyl,acrylamide, alkyl acrylamide, dialkyl acrylamide, methacryloyl, allyl,vinyl, styrenyl, or a combination thereof.
 5. The composition of claim1, wherein the actinically-crosslinkable polysiloxane-polyglycerol blockcopolymer is defined by Formula I:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and J¹ are,independently, alkyl, cycloalkyl, aryl, alkylpolyethylene oxide, orpolyglycerol, any of which is optionally substituted with halide,hydroxy, thiol, carbonyl, alkoxy, alkylhydroxy, carboxyl, amino, amido,alkyl, alkenyl, alkynyl, aryl, —NR^(x)R^(y), —C(O)NR^(x)R^(y), azide, ora combination thereof; Q¹ and Q² are independently H, OH, amino, alkyl,alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, or heteroaryl, any ofwhich is optionally substituted with epoxy, hydroxy, thiol, carbonyl,alkoxy, alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl,aryl, —NR^(x)R^(y), —C(O)NR^(x)R^(y), azide, or a combination thereof;R^(x) and R^(y) are independently H, OH, alkyl, alkenyl, alkynyl,cycloalkyl, aryl, alkylaryl, or heteroaryl; Cure Group comprises theethylenically unsaturated group; a, c, d, e, f, g, h, i, j, and k are,independently, an integer from 0 to 10,000; with the proviso that: atleast one of e, g, h, and j is not 0, and at least one of d, f, i, and kis not 0; and b is an integer from 1 to 10,000.
 6. The composition ofclaim 5, wherein: R¹-R¹¹ and J¹ are, independently, C₁-C¹⁸ alkyl, C₃-C¹⁸cycloalkyl, C₃-C₂₀ aryl, alkylpolyethylene oxide, or polyglycerol, anyof which is optionally substituted; and Q¹ and Q² are independentlyC₁-C₁₈ alkyl, C₃-C₂₀ aryl, C₁-C₁₈ perfluoroalkyl, C₁-C₁₈ alkanol, C₁-C₁₈alkylthiol, C₁-C₁₈ alkylamine, C₁-C₁₈ dialkylamine, any of which isoptionally substituted.
 7. The composition of claim 5, wherein the CureGroup is selected from the group consisting of:

wherein R^(a) is H, alkyl, or cycloalkyl, either of which is optionallysubstituted with halide, hydroxy, alkylthiol, carbonyl, alkoxy,alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,—NR^(x)R^(y), —C(O)NR^(x)R^(y), or a combination thereof; and R^(x) andR^(y) are independently H, OH, alkyl, alkenyl, alkynyl, cycloalkyl,aryl, alkylaryl, or heteroaryl.
 8. The composition of claim 1, whereinthe polysiloxane prepolymer comprises polydimethylsiloxane.
 9. Thecomposition of claim 1, wherein the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer is defined by Formula IX:

wherein a, c, e, f, i, j and k are, independently, an integer from 0 to10,000; with the proviso that: at least one of e and j is not 0, and atleast one of f, i, and k is not 0; and b is an integer from 1 to 10,000.10. The composition of claim 1, wherein the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer is defined by Formula X:

wherein a, c, e, f, i, j and k are, independently, an integer from 0 to10,000; with the proviso that: at least one of e and j is not 0, and atleast one of f, i, and k is not 0; and b is an integer from 1 to 10,000.11. The composition of claim 1, wherein the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer is defined by Formula XI:

wherein a, c, e, f, i, j and k are, independently, an integer from 0 to10,000; with the proviso that: at least one of e and j is not 0, and atleast one of f, i, and k is not 0; and b is an integer from 1 to 10,000.12. The composition of claim 1, wherein the actinically-crosslinkablepolysiloxane-polyglycerol block copolymer comprises a methacrylatedpolydimethylsiloxane-polyglycerol block copolymer; a chain extendedactinically-crosslinkable polysiloxane-polyglycerol block copolymer; ora combination thereof.
 13. The composition of claim 1, wherein theactinically-crosslinkable polysiloxane-polyglycerol block copolymercomprises a chain extended actinically-crosslinkablepolysiloxane-polyglycerol block copolymer and the chain extendedactinically-crosslinkable polysiloxane-polyglycerol block copolymer isdefined by Formula XII:

wherein R¹, R^(1′), R², R^(2′), R³, R^(3′), R⁴, R^(4′), R⁵, R^(5′), R⁶,R^(6′), R⁷, R^(7′), R⁸, R^(8′), R⁹, R^(9′), R¹⁰, R^(10′), R¹¹, R^(11′),J¹, and J^(1′) are, independently, alkyl, cycloalkyl, aryl,alkylpolyethylene oxide, or polyglycerol, any of which is optionallysubstituted with halide, hydroxy, thiol, carbonyl, alkoxy, alkylhydroxy,carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl, —NR^(x)R^(y),—C(O)NR^(x)R^(y), azide, or a combination thereof; Q¹, Q^(1′), Q², andQ^(2′) are independently H, OH, amino, alkyl, alkenyl, alkynyl,cycloalkyl, aryl, alkylaryl, or heteroaryl, any of which is optionallysubstituted with epoxy, hydroxy, thiol, carbonyl, alkoxy, alkylhydroxy,carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl, —NR^(x)R^(y),—C(O)NR^(x)R^(y), azide, or a combination thereof; R^(x) and R^(y) areindependently H, OH, alkyl, alkenyl, alkynyl, cycloalkyl, aryl,alkylaryl, or heteroaryl; Cure Group and Cure Group′ independentlycomprise an ethylenically unsaturated group; Z is a chain extensiongroup; a, a′, c, c′, d, d′, e, e′, f, f′, g, g′, h, h′, j, j′, k, and k′are, independently, an integer from 0 to 10,000, with the proviso that:at least one of e, g, h, and j is not 0, at least one of e′, g′, h′, andj′ is not 0, at least one of d, f, i, and k is not 0, and at least oneof d′, f′, i′, and k′ is not 0; and b and b′ are independently aninteger from 1 to 10,000.
 14. The composition of claim 13, wherein:R¹-R¹¹, R^(1′)-R^(11′), J¹, and J^(1′) are, independently, C₁-C₁₈ alkyl,C₃-C₁₈ cycloalkyl, C₃-C₂₀ aryl, alkylpolyethylene oxide, orpolyglycerol, any of which is optionally substituted; and Q¹, Q^(1′),Q², and Q^(2′) are independently H, OH, aryl, epoxide, alkanol,alkylthio, alkenylthio, arylthio, amine, alkylamine, dialkylamine,(meth)acrylate, (meth)acrylamide, dialkyl (meth)acrylamide, vinyl,ketone, aldehyde, carboxylic acid, anhydride, or azide, any of which isoptionally substituted.
 15. The composition of claim 13, wherein CureGroup and Cure Group′ are independently selected from the groupconsisting of:

wherein R^(a) is H, alkyl, or cycloalkyl, either of which is optionallysubstituted with halide, hydroxy, alkylthiol, carbonyl, alkoxy,alkylhydroxy, carboxyl, amino, amido, alkyl, alkenyl, alkynyl, aryl,—NR^(x)R^(y), —C(O)NR^(x)R^(y), or a combination thereof; and R^(x) andR^(y) are independently H, OH, alkyl, alkenyl, alkynyl, cycloalkyl,aryl, alkylaryl, or heteroaryl.
 16. A silicone hydrogel compositioncomprising the composition of claim 1 crosslinked with a crosslinker.17. An interpenetrating polymer network comprising the composition ofclaim 1 crosslinked with a crosslinker in the presence of an initiator,a hydrophilic monomer, a hydrophobic monomer, an amphiphilic monomer, azwitterionic monomer, a UV-blocker, a blue light blocker, anantimicrobial monomer, a dye, a pigment, a solvent, or a combinationthereof.
 18. A method of use of the composition of claim 1 in a medicaldevice, in an ophthalmic device, as a coating for a medical device, as awound dressing, or a combination thereof.
 19. A contact lens comprisingthe composition of claim 1, wherein the contact lens comprises a soft,hydrophilic contact lens.
 20. The contact lens of claim 19, wherein thecontact lens exhibits hydrophilic surfaces without a post-curing surfacetreatment.